metal-organic compounds Acta Crystallographica Section C Crystal Structure Communications
4_英寸GaN_衬底MOCVD_外延高质量AlGaN
4英寸GaN衬底MOCVD外延高质量AlGaN/GaN HEMT材料研究分析高 楠 房玉龙* 王 波 张志荣 尹甲运 芦伟立 陈宏泰 牛晨亮（河北半导体所）摘 要：本文对金属有机物化学气相淀积法在4英寸GaN衬底上生长出的高质量AlGaN/GaN HEMT外延材料进行了研究分析。
生长过程采用NH3/H2混合气体及H2交替通入的方法对衬底表面进行了预处理，阻隔了界面杂质的扩散。
得益于衬底与外延的高度晶格匹配，GaN材料的螺位错密度降低到1.4×107cm-2，刃位错密度降低到3.0×106cm-2；非接触霍尔测试仪结果显示二维电子气迁移率为2159 cm2/V·s ，说明制备的材料晶体质量高且电学性能优异。
此外，由于衬底与外延之间不存在热失配，使用拉曼光谱仪发现同质外延的GaN E2（TO）峰位与衬底的E2（TO）峰位完全重合，表明同质外延过程中无应力应变产生。
关键词：GaN衬底，AlGaN/GaN HEMTStud y of High-quality AlGaN/GaN HEMT Homo-epitaxial Material on4-inch GaN Substrate by MOCVDGAO Nan FANG Yu-long* WANG Bo ZHANG Zhi-rong YIN Jia-yun LU Wei-liCHEN Hong-tai NIU Chen-liang（Hebei Semiconductor Research Institute）Abstract:High-quality AlGaN/GaN HEMT homo-epitaxial material grown on 4-inch GaN homo-substrate by metal-organic chemical vapor deposition (MOCVD) was studied in this paper. An alternation gas model of ammonia/ hydrogen (NH3/H2) mixed gas and H2 gas was employed to thermal treatment of GaN homo-substrate to prevent the spread of impurities. Due to the match of lattices, the density of screw dislocation was as low as 1.4×107cm-2 and the density of edge dislocation reached 3.0×106cm-2. The contactless Hall test results showed that the AlGaN/GaN HEMT material had a two-dimensional electron gas (2DEG) mobility of 2159 cm2/V•s, indicating that the homo-epitaxial AlGaN/GaN HEMT material has high quality and good electrical performance. In addition, thanks to the absent thermal mismatch during the growth, the Raman spectrum test manifested that the peak positions of E2-high for GaN homo-substrate and the epitaxial material were totally coincident, showing that there was no strain in the homo-epitaxial growth.Keywords: GaN substrate, AlGaN/GaN HEMT作者简介：高楠，硕士，工程师，主要研究方向为宽禁带半导体材料生长及相关技术。
金属有机
Chemical Engineering Journal 171 (2011) 517–525Contents lists available at ScienceDirectChemical EngineeringJournalj o u r n a l h o m e p a g e :w w w.e l s e v i e r.c o m /l o c a t e /c ejSynthesis,characterization and hydrogen adsorption on metal-organic frameworks Al,Cr,Fe and Ga-BTBDipendu Saha ∗,Renju Zacharia,Lyubov Lafi,Daniel Cossement,Richard ChahineInstitut de recherche sur l’hydrogène,Universitédu Québec àTrois-Rivières,Trois-Rivières,QC G9A 5H7,Canadaa r t i c l ei n f oArticle history:Received 21February 2011Received in revised form 7April 2011Accepted 8April 2011Keywords:Metal-organic framework (MOF)BTB ligand Pore textureSpecific surface area Hydrogen adsorptiona b s t r a c tBenzenetribenzoate (BTB)ligand is combined with four trivalent metals,Al,Cr,Fe and Ga by solvothermal synthesis to form four different metal-organic frameworks (MOFs),abbreviated as M-BTB,where M stands for the metal.Each of the MOFs is characterized with pore texture,scanning electron microscopic images (SEM),X-ray diffraction (XRD),Fourier transform infra-red spectroscopy (FT-IR)and thermogravimetric analysis (TGA).Pore texture reveals the highest BET surface area belongs to Al-BTB (1045m 2/g)and decreases in the order of Cr >Fe >Ga.Hydrogen adsorption at 77K and up to ambient pressure indicates that Al-BTB adsorbs highest amount of H 2(0.98wt.%)and decreases in the same order as the specific surface areas.High pressure H 2adsorption at room temperature (298K)and pressure up to 80bar reveals that Fe-BTB adsorbs highest amount of hydrogen (0.51wt.%or 2.75g L −1,absolute)and the adsorption amount decreases in the order of Cr >Al >Ga.© 2011 Elsevier B.V. All rights reserved.1.IntroductionMetal-organic frameworks (MOFs)are highly promising adsor-bents because of their very high specific surface area,tunable pore size and case-specific tailoring of basic molecular architec-ture leading to the large and selective adsorption capacities of several gas molecules.A large volume of MOFs has been reported in the literature;most of them were synthesized and decorated accordingly with an aim towards gas storage [1–3],separation [4],heterogeneous catalysis [5],drug delivery [6]or molecular sens-ing [7].Topologically,all the MOFs consist of metal centers,more precisely known as secondary building units (SBUs)connected with each other by the organic molecules,commonly known as organic linkers [8].Different types of metals have been employed and examined for the structure forming capacity of MOFs;typical examples are zinc [9–15,28],copper [16,17],chromium [18–20],aluminum [21,22],iron [23,24],scandium [25],manganese [26],zirconium [27],vanadium [29]or cadmium [42].Organic linker is probably the far most important part in tai-loring the architecture of metal-organic frameworks.The linker molecule plays the role to tune the pore size and specific sur-face area of the MOFs.Most versatile usages of different organic molecules as linkers were noticed in synthesizing different species of IRMOFs where zinc was employed as part of secondary build-ing units [8,28].Benzenedicarboxylic acid (BDC)or terephthalic∗Corresponding author.Tel.:+18652422221;fax:+18655768424.E-mail address:dipendus@ (D.Saha).acid is most common in synthesizing different species of MOFs,including MOF-5[9,13,28],MIL-53(Cr,Al or Fe)[19,29]or MIL-101[20,30,31].However,the reported large surface area and the maxi-mum gas (H 2and CO 2)uptake is observed for benzenetribenzoic acid (BTB)as organic linker that formed metal-organic frame-work,MOF-177with zinc as SBU former [10–12,14,15,33–35].Besides hydrogen and carbon dioxide,methane [36],nitrous oxide [36]and carbon monoxide [37]adsorption was also exam-ined on MOF-177.In recent time,Furukawa et al.incorporated few other ligands,like 4,4 ,4 -(benzene-1,3,5-triyl-tris(ethyne-2,1-diyl))tribenzoate (BTE),4,4 ,4 -(benzene-1,3,5-triyl-tris(benzene-4,1-diyl))tribenzoate (BBC)or biphenyl-4,4 -dicarboxylate (BPDC)that demonstrated even larger surface area than BTB containing ligands [38].Apart from the usage of pure or only one type of ligand,employing more than one ligand to form a single MOF was reported recently.Koh et al.[39]combined BDC and BTB lig-ands in different proportions to form different species of MOFs and it was reported that between the ratio of 6:4and 5:5of BDC over BTB,a new type of mesoporous MOF was generated and has been named as UMCM-1.Saha and Deng [40]also gen-erated two types of hybrid MOFs consisting of BDC and BTB by employing two different solvents,DMF (N,N,dimethylformaide)and DEF (N,N,diethylformaide).In other work,Koh et al.[41],syn-thesized the hybrid MOF (UMCM-2)with the combination of BTB and thieno[3,2-b]thiophene-2,5-dicarboxylate (T 2DC)in 1:1ratio,that possesses the BET surface area of more than 5000m 2/g.Klein et al.[43]synthesized the hybrid mesoporous MOF DUT-6with BTB and NDC (2,6-naphthalenedicarboxylate)in 3:2mole ratio that possesses high pore volume of 2.02cm 3/g.Despite the ubiquitous1385-8947/$–see front matter © 2011 Elsevier B.V. All rights reserved.doi:10.1016/j.cej.2011.04.019518 D.Saha et al./Chemical Engineering Journal 171 (2011) 517–525Table 1Synthesis conditions of the metal-organic frameworks.MOF identityMetal saltsSalts amount (g)BTB amount (g)Thermal conditionsAl-BTB Al(NO 3)3·9H 2O 0.1710.290◦C,24h Cr-BTB Cr(NO 3)3·9H 2O 0.1820.290◦C,24h Fe-BTB Fe(NO 3)3·9H 2O 0.2700.280◦C,3days Ga-BTBGa(NO 3)3·x H 2O0.2550.2100◦C,24hevidence that BTB ligand could provide high surface area and gas adsorption properties,it was not employed to form MOFs with any other metal,till today.In this work,we combined BTB ligand with four differ-ent trivalent metals,aluminium,chromium,iron and gallium to form four types of metal-organic frameworks.Each type of MOF was performed materials characterization with pore tex-ture,density measurement,scanning electron microscopy (SEM),Fourier-transform infra-red (FT-IR)spectra,thermogravimetric analysis (TGA)and X-ray diffraction to reveal the identity of the crystals.Hydrogen adsorption measurement was performed at 77K and room temperature to examine the hydrogen sorption capacity of those MOFs.2.Experimental methods2.1.Synthesis of Al,Cr,Fe and Ga-BTBAll metal-organic frameworks of this present work were syn-thesized by solvothermal technique.In general,the corresponding metal salts or the metal precursors were dissolved in 25mL ethanol,where as the BTB ligand was dissolved in 10mL N,N-dimethylformamide (DMF)followed by mixing the two solutions and subjecting to thermal treatment.For Ga-BTB,both the pre-cursor and the ligand were dissolved in 35mL of DMF as the Ga precursor was sparingly soluble in ethanol.The exact identity of metal precursor,amounts of reagents and the thermal conditions are revealed in details in Table 1.After the thermal treatment,the crystals were separated from the solution and washed twice with DMF in order to remove any unreacted reagent.Finally,the DMF treated samples were washed several times with chloroform min-imize the DMF level within the crystals and stored inside glovebox under argon atmosphere in closed container.2.2.Materials characterizationsThe materials characterizations techniques employed for each sample include pore textural properties,density measurement,Fourier-transform infra-red spectroscopy (FT-IR),thermo gravi-metric analysis (TGA),scanning electron microscopy (SEM)and X-ray diffraction technique.The pore textural properties were calculated by nitrogen adsorption–desorption study at liquid nitrogen temperature (77K)and pressure up to 1bar in Micromeritics ASAP 2020instrument.The pore textural properties BET surface area and pore size distribu-tion by density functional theory (DFT)were obtained by analyzing the nitrogen adsorption and desorption isotherms with the built-in software in the ASAP 2020surface area and porosity analyzer.The adsorbent samples were degassed ex-situ at 373K for 24h toa bcd10.80.60.40.20Relative pressure (P/Po)N i t r o g e n a d s o r b e d (m m o l /g )10.80.60.40.20Relative pressure (P/Po)N i t r o g e n a d s o r b e d (m m o l /g )10.80.60.40.20Relative pressure (P/Po)N i t r o g e n a d s o r b e d (m m o l /g )10.80.60.40.2Relative pressure (P/Po)N i t r o g e n a d s o r b e d (m m o l /g )Fig.1.N 2adsorption–desorption plot of Al-BTB (a),Cr-BTB (b),Fe-BTB (c),Ga-BTB (d).D.Saha et al./Chemical Engineering Journal171 (2011) 517–525519remove the guest molecules from the samples before the nitrogen adsorption measurements.The FT-IR spectra of the samples were measured in Thermo-Scientific Nicolet iN10-MX FT-IR chemical imaging microscope within the wave numbers of4000–800cm−1.The sample prepa-rations include grinding and mixing with KBr followed by pelletization before introducing to the laser.Scanning electron microscopy images(SEM)images were recorded by employing JEOL JSM-5500instrument by using an accelerating voltage of18kV.The thermogravimetric analysis(TGA)was performed in Perkin Elmer TGA7Instrument.The temperature ramp rate employed for this study was10◦C/min up to800◦C in an inert gas(Ar)flow.The X-ray data were recorded in Bruker D8Advance X-ray diffractometer with Cu K␣emission( =1.54056˚A).For each sample,the XRD scan was performed from2◦to75◦with0.02◦width and1s count time.Pro-cessing of all diffraction data including structure refinement was performed using JADE8+software supplied by Materials Data Inc. (Livermore,CA,USA).2.3.Hydrogen adsorption measurementHydrogen adsorption at low(up to1bar)pressure and at77K was measured volumetrically in ASAP2020instrument.About 50mg of each of the sample was used in this experiment.The adsor-bent sample was degassed under a vacuum and at373K for24h before the hydrogen adsorption measurement.Ultra-high purity hydrogen(Praxair Inc.)was introduced into a separate gas port of the adsorption unit for the hydrogen adsorption measurements.The high pressure hydrogen adsorption was measured in Sieverts-type volumetric apparatus,built and calibrated in our laboratory.About100mg of sample was introduced within the sample container and it was subjected to room temperature out-gassing at10−3Torr by employing a turbomolecular pump before any measurement.The skeleton density of the samples were mea-sured by admitting ultra-high purity helium gas(Praxair Inc.) in to the system and performing the density measurement at ambient temperature and equilibrium pressure less than20bar in order to minimize the effect of helium adsorption.The tem-perature and pressure of the gas were monitored by employing calibrated Guildline9540digital platinum resistance temperature detector(accuracy=±0.01◦C)and Paroscientific740digiquartz high accuracy digital pressure gauge(accuracy=0.01%at f.s.).The real gas densities were obtained from the NIST-12standard ref-erence database.The sample skeleton densities were calculated from the linear regression of sample mass versus gas density plots. Hydrogen adsorption isotherms were measured by using ultra-high purity hydrogen gas(Praxair Inc.).The excess gas adsorption was measured at room temperature(298K)and pressure up to80bar. To estimate the order of uncertainties that might arise from our adsorption measurement,we performed a skeleton density and hydrogen adsorption measurement of similar masses of activated carbon AX-21,whose adsorption characteristics are well-known. The maximum uncertainty of our experiments was found to be not more than±3%.The measured leak rate on this system is practically negligible:10−6MPa/s with He gas at4MPa and room temperature. Leak measured using Mathewson Leak hunter plus8066yielded no leak with hydrogen gas at5MPa and room temperature(minimum detectable leak of the instrument is8.1×10−6mL s−1of hydrogen).3.Results and discussions3.1.Materials characterizations3.1.1.Pore texture and densityThe pore texture properties including BET specific surface area and pore size distribution were calculated from nitrogen Table2Pore texture properties.MOF identity BET SSA(m2g−1)Bulk density, b(g cm−3)Skeleton density,s(g cm−3)Al-BTB10450.30 1.72Cr-BTB5520.54 1.96Fe-BTB3620.33 1.17Ga-BTB620.29 2.865adsorption–desorption plot by employing the built-in software of Micromeritics ASAP2020porosity and surface area analyzer(shown in Fig.1(a)–(d)).The bulk density was measured in ASTM standard D2854-96where as the skeleton density was measured by helium expansion experiment at ambient temperature.The pore texture and density values of all the samples are shown in details in Table2. It is observed that the highest BET SSA(1045m2g−1)were achieved for aluminum(Al)sample.The surface areas decrease in the order of Cr>Fe>Ga.The pore size distribution calculated by density func-tional theory(DFT)for all the samples are shown in Fig.2(a)and (b)for differential and cumulative pore volume,respectively.It is observed almost all the MOFs possess very narrow distribution in the microporous region,though majority of the pore volumes con-tribute in the mesopore region.Al-BTB possesses two peaks,8.58˚A and11.79˚A though the large pore volume arises from pores in the region of120˚A.Cr-BTB shows the presence of pores in8.58˚A and 12.69˚A but also shares large pore volume in less than100˚A.Fe-BTB is having very low pore volume in microporous region of8˚A and 12.69˚A but having very large pore volume in the range of160˚A. Amongst all the MOFs,Ga-BTB shows the lowest available pore volume,narrow micropore in12.69˚A,but larger pore volume in <200˚A.It is also clear that these MOFs posses the micropore width in the range of8–12˚A along with large mesopores which may arise due to possible crystalline defects.The total pore volume is highestabPore width (Å)Differentialporevolume(cc/g-Å)Pore width (Å)Cumulativeporevolume(cc/g)Fig.2.(a)Differential pore size distribution by DFT theory.(b)Cumulative pore size distribution by DFT theory.520 D.Saha et al./Chemical Engineering Journal 171 (2011) 517–525Fig.3.Scanning electron images,Al-BTB (a),Cr-BTB (b),Fe-BTB (c)and Ga-BTB (d).for Al-BTB followed by Cr-BTB,Fe-BTB and Ga-BTB as observed in Fig.2(b).It is noticeable that the specific surface areas of all the samples are lower than MOF-177[11,12]or other BTB contain-ing hybrid MOFs [39,41,43].Most probably,the presence of two or more interwoven three-dimensional nets within MOF structures lowered their porosity as observed in the case of PCN-6[44]or MOF-14[Cu 3(BTB)2][45].However,the specific surface areas of Al-BTB is higher than several other mesoporous MOFs reported till today,like JUC-48[42].The Cr-BTB sample attained the largest bulk density of 0.54g cm −3.For all the remaining samples,the bulk density lies in the close region of 0.29(Ga)to 0.33g cm −3(Fe).The skeleton den-sity was observed to be highest for Ga sample (2.86g cm −3).Lower values of skeleton were densities achieved for Al (1.72g cm −3),Fe (1.17g cm −3)and Cr (1.96g cm −3)based samples.3.1.2.Scanning electron microscopy (SEM)The scanning electron microscopic (SEM)images for Al,Fe,Cr and Ga samples are shown in Fig.3(a)–(d),respectively.All the images were taken after outgassing the MOFs at elevated tem-perature.The morphology of the crystallites is not quite well distinguishable for all samples,most probably because of the lower magnification power of our SEM microscope.For Ga sample,the crystallites look quite close to the hexagonal profile with size range from 0.5m in the face to 0.13m in width.The crystallites of Fe sample resemble cubic or orthogonal nature with average size 0.33m.The exact morphology of Al and Cr samples was not possi-ble to determine with the present SEM image,however,the average size of the crystals could be approximated as 0.1–0.15m for Cr and 0.07–0.13m for Al samples.3.1.3.X-ray diffractionThe X-ray diffraction patterns of the four samples are shown in Fig.4.It is observed that the sharpest peak of all the MOFsisAngle(2θo)I n t e n s i t y (c o u n t s )Fig.4.X-ray diffraction patterns.D.Saha et al./Chemical Engineering Journal 171 (2011) 517–525521I n t e n s i t y (a .u .)located at around 6◦followed by a shorter peak at an angle of 11◦.There are also some broad peaks located at higher angles of all the samples.Al and Cr-BTB possess the broad peak at an angle 19–20◦,where as Ga sample shows two small but broad peaks at 35◦and 64◦.Al-BTB possesses a broad peak at an angle of 44◦and a small peak at the shorter angle of 3.4◦.For Fe-BTB,two broader peak formations are also located at 33◦–34◦and 44◦–45◦.Unlike MOF-177or UMCM-1,none of our samples shows the largest peak at 4◦–5◦(MOF-177[12])or 2◦–3◦(UMCM-1[39]),however,all the samples possess the largest peak at 6◦–7◦,similar to that of UMCM-2[41].It is also noticeable that almost all of the peaks of each of the pattern are quite broad in nature accompanied by quite heavy noise and low intensity.Most probably,very thin layer of chloro-form was still present in the inter-lattice spaces of crystals that prohibited the penetration of X-ray within it as described by Saha and Deng [32].The wide pore opening of the mesoporous mate-rials may also caused the partial collapse of the crystalline lattice after the removal guest species during the outgassing phase at ele-vated temperature,as suggested by Koh et al.[39]or observed in the XRD pattern of the mesoporous MOF composed of Al III with one or bidentate ligand comprising of six membered aro-matic rings [46].Due to the poor peak profile and possible lack in accuracy in the overall pattern,we did not attempt to index the peaks and hence did not report the crystal phase identification data.3.1.4.FT-IR spectraThe FT-IR spectra of the four metal-organic frameworks are pro-vided in Fig.5.The overall patterns are in quite well agreement with other BTB containing MOFs,reported elsewhere [14,47].The sharp peak at 1400cm −1region is attributed to the symmetric stretching of C O bond that belongs to the carboxylate group of the BTB ligand,where as the peak at 1600cm −1is originated from the asymmetric stretching of the same bond [47].The few weak peaks at 1300–1000cm −1can be attributed to the in-plane bend-ing vibrations of aromatic C–H bonds and the remaining smaller angle peaks (1000–800cm −1)could be contributed by the out of plane bending vibration of C–H bonds [14,47].The C C stretch-ing vibration from the benzene ring of the BTB ligand appears as a weak peak at 1520–1570cm −1.Few weak peaks starting after 1600cm −1till 2000cm −1are attributed to the first overtone of in-plane and out of plane vibrations of C–H bonds of BTB ligand,where as the second overtone appears at 2600–2100cm −1.Very broad and weak peak formation in the region of 3000cm −1is attributed to the aromatic C–H stretching of the BTB ligand [14].Finally,the absence of any strong peak at 1700cm −1provides the clear indi-0102030405060708090100ab0200400600800w t .%-8-7-6-5-4-3-2-100100200300400500600700800Tempe rature (o C)D i f f e r e n t i a l -w t .% (d w t .%/d t )Fig.6.Thermogravimetric analysis (TGA),linear form (a)and differential form (b).cation of absence of any free carboxylic acid in the MOF samples[14].3.1.5.Thermogravimetric analysis (TGA)The thermogravimetric plots in linear and differential form are shown in Fig.6(a)and (b).From the differential plot,the losses in weight can be localized in the three discrete regions of 50–100◦C,150–250◦C and 500–600◦C.Very minute loss is observed around in the first region of 50–100◦C (1–2wt.%)that can be contributed to the desorption of adsorbed gas from their pore spaces.In the sec-ond region,150–250◦C,the cause of mass loss is attributed to the removal of guest species,mostly N,N dimethylformamide (DMF).For Cr,Fe and Ga based samples,the loss is in this region is lim-ited to 6–7wt.%unlike Al species that suffered a significant loss of 19wt.%.This higher loss is a clear indication of larger occupancy of guests within the Al based MOF that could provide better pore texture if it were outgassed at elevated temperature and/or with elongated time period.The final region of loss at 500–600◦C can be attributed to the disintegration of framework,i.e.,the decomposi-tion of BTB ligand itself.From the differential plot,the loss can be quantified approximately as 31,15,49and 34wt.%for Al,Cr,Fe and Ga based MOFs,respectively.The final residue amount was within 30–45wt.%for all the samples that can be attributed to the oxides of the corresponding metals.The weight loss due to the decompo-sition BTB ligand is much smaller compared to the possible overall proportion of BTB in the MOF resulting in quite higher final residue than expected for a metal oxide.Most probably,there was a sig-nificant amount of carbon deposition,originated from the organic ligand,on the metal oxides as the TGA measurement was performed in an inert atmosphere.522D.Saha et al./Chemical Engineering Journal 171 (2011) 517–525Pressure (Torr)H 2 a d s o r b e d (w t .%)Fig.7.Low pressure hydrogen adsorption isotherms.4.Hydrogen adsorption properties4.1.Low pressure hydrogen adsorptionThe low pressure hydrogen adsorption for all the MOFs were measured at liquid nitrogen temperature (77K)and pressure up to 800Torr in ASAP 2020instrument.The hydrogen adsorption isotherms are shown in Fig.7.All the isotherms are typically type-I according to IUPAC classifications.The highest adsorption is exhib-ited by Al-MOF,around 0.98wt.%,followed by Cr (0.76wt.%),Fe(0.67wt.%)and Ga (0.36wt.%).It is observed that the hydrogen uptake at ambient pressure range was dictated by BET specific sur-face area as the hydrogen adsorption amount decreases exactly in the same as BET SSA (Al >Cr >Fe >Ga)as observed in Table 2.The lower hydrogen uptake of all of these samples compared to MOF-177or several other BTB containing MOFs can be attributed to the lower porosity of the materials that is probably caused by the interwoven 3D nets within the structures as described earlier.All the hydrogen adsorption isotherms were modeled by four well-known equations,Langmuir,Freundlich,Sips (Langmuir–Freundlich)and Toth models [12,13].The Langmuir isotherm can be written as:q =a m bP 1+bP(1)where q (wt.%)is the adsorbed hydrogen amount,p is the hydro-gen pressure (Torr),a m (wt.%)is the monolayer adsorption capacity and b (Torr −1)is the other Langmuir isotherm equation parameter.Both equation parameters can be determined from the slope and intercept of a linear Langmuir plot of (1/q )versus (1/p ).Freundlich isotherm is given by:q =kP 1/n(2)where k and n are the Freundlich isotherm equation parameters that can be determined by the slope and intercept of ln P versus ln q plot.The Sips (Langmuir–Freundlich)model can be written asq =a m bP (1/n )1+bP (1/n )(3)where a m ,b and n are equations constants.a cb dPressue (Torr)H 2 a d s o r b e d (w t %)00.10.20.30.40.50.60.70.8800700600500400300200100Pressure (Torr)H 2 a d s o r b e d (w t .%)00.10.20.30.40.50.60.70.8Pressure (Torr)H 2 a d s o r b e d (w t .%)Pressure (Torr)H 2 a d s o r b e d (w t .%)Fig.8.Isotherm model fitting,Al-BTB (a),Cr-BTB (b),Fe-BTB (c)and Ga-BTB (d).D.Saha et al./Chemical Engineering Journal 171 (2011) 517–525523Table 3Parameters of isotherm model fitting.Isotherm modelModelparameters Parametervalues (Al-BTB)Parameter values (Cr-BTB)Parameter values (Fe-BTB)Parameter values (Ga-BTB)ARE%(Al-BTB)ARE%(Cr-BTB)ARE%(Fe-BTB)ARE%(Ga-BTB)Langmuir modela m 1.1580.82510.7120.378 1.4561.631.5940.622b0.0060.0090.0100.016Freundlich modelk 0.0660.0840.0910.082 1.7010.8030.4870.367n2.4272.9833.2974.401Sips modela m 1.533 2.473 2.526 1.2880.2510.4140.2390.257b 0.0120.0260.0300.059n1.3322.3582.6723.483Toth model˛T 5.340 4.972 4.919 5.2680.8290.3270.1630.257k T 2.595 1.347 1.0250.463t0.2450.1810.1560.086The Toth model can be given byq =˛T p (k T +p t )(1/t )(4)where ˛T ,k T and t are Toth equation constants.All the equation parameters of Sips and Toth model can be calculated by non-liner regression techniques.The degree of model fitting was compared by the absolute relative error (ARE)percent,calculated asARE%=Nn =1|x exp −x mod |N×100%(5)where x exp is the experimental point,x mod is the modeling point and N is the number of points in the isotherm.These parameters are given in Table 3and model fitting plots are shown in Fig.8(a)–(d)for Al,Cr,Fe and Ga samples,respectively.ARE values confirmed that Sips model fit better for Al-BTB,however,Toth model fits best for the rest of MOFs.4.2.High pressure hydrogen adsorptionThe high pressure adsorption of four MOFs at room tempera-ture (298K)and pressure up to 80bar is shown in Fig.9(a)and (b)for gravimetric and volumetric capacities,respectively.The excess adsorption amount was directly obtained from the instru-ment shown as the symbols in the plots.Assuming the adsorbed the gas density is equivalent to the liquid density of the same species (hydrogen),the absolute adsorption amount can be calculated as [11,12]m abs =m excess1−( (T,P )/ (l ))(6)where (T ,P )is density of the adsorptive gas (hydrogen)at the particular temperature and pressure and (l )is the density of the same gas in the liquid phase.The absolute adsorption was repre-sented as continuous curve in the plots.It is clearly observed that the Fe-BTB performs highest hydrogen uptake both gravimetri-cally (abs:0.51wt.%,excess:0.465wt.%)and volumetrically (abs:2.75g L −1,excess:2.51g L −1).The hydrogen uptake amounts of the remaining samples lie in the similar range,however,minute observation reveals that the uptake capacity decreases in the order of Cr (0.42wt.%,1.38g L −1)>Al (0.25wt.%,0.85g L −1)>Ga (0.27wt.%,0.8g L −1),all absolute amount.It is also noticeable that the hydrogen adsorption increases linearly with pressure similar to that of many other types of MOFs,which are caused by the poor adsorbate–adsorbent interactions at the ambient temperature level.It is evident that the hydrogen adsorption amounts at elevated pressure and at ambient temperature were not controlled by the pore texture properties unlike the adsorption at ambient pressureabPressure (bar)H 2 a d s o r b e d (w t .%)Pressure (bar)H 2 a d s o r b e d (g L -1)Fig.9.High pressure hydrogen adsorption,gravimetric adsorption amount (a)andvolumetric uptake amount (b).and 77K temperature which are quite obvious due to the associ-ated mesoporosity of these MOFs.The significant higher adsorption by Fe-BTB over the rest of the MOFs is most probably caused by the possible open or unsaturated metal sites that could be created during the evacuation step by the elimination of one or more sol-vent molecules from the MOF cavities [48].The unsaturated metal sites can increase the electrostatic attraction between hydrogen and partial charges on metal-organic framework atoms thereby dominating the key adsorption mechanism.5.ConclusionIn this work,we synthesized four metal-organic frameworks by the incorporation of benzenetribenzoate (BTB)ligand with four。
金属有机化合物
基
如：CH2SiMe3 或CH2Ph
② “阻断”β－H转移： 吸电子基或π酸作为配体
例如：Ti(CH3)4在－50℃时也有些分解， 而Ti(bipy)（CH3）2直到30 ℃都稳定存在。
M
N(CH3)2 CH2
N
2RP
PR2
2 HC
C H2
M
H2 C
CH2
M
N(CH3)2
C H2
H.Schmidbauer et al., Angew,Chem.,Int.Ed.,17,126(1978);Acc.Chem.Res.,8,62(1975)
③大多数配合物都服从有效原子序数规则。
2.羰基化合物的制备
(1)金属粉末与CO直接作用 如四羰基合镍、五羰基合铁的合成。金属粉末必须是新鲜 还原出来的处于非常活化的状态才行。
Ni＋4CO 常温常压 Ni(CO)4(m.p.－25℃) △ Ni＋4CO
Fe＋5CO 493K , 20MPa Fe(CO)5
①金属与CO之间的化学键很强。如在Ni(CO)4中，Ni－ C键能为147 kJ·mol－1，这个键能值差不多与I－I键能(150 kJ·mol－1)和C－O单键键能(142 kJ·mol－1)值相差不多。
②在这类配合物中, 中心原子总是呈现较低的氧化态( 通常为0，有时也呈较低的正氧化态或负氧化态)。氧化态 低使得有可能电子占满d－MO, 从而使M→L的电子转移 成为可能。
2、实际应用：广泛的应用，最突出的是用作 催化剂
目前，金属有机化学已成为无机化学、有机化学、结 构化学、配位催化以及生物化学等多种学科相互渗透、 共同研究的重要领域。
4. 金属有机化合物的特点
成键类型： 是经典的化学键理论无法说明的
ferrocenecompounds.xxxix
metal-organic compoundsm328#2003International Union of CrystallographyDOI:10.1107/S0108270103011703Acta Cryst.(2003).C 59,m328±m330Ferrocene compounds.XXXIX.11-FerrocenylisochromaneMario Cetina,a Senka akovicÂ,b Vladimir Rapic Âb *and Amalija GolobicÏc aFaculty of Textile Technology,University of Zagreb,Pierottijeva 6,HR-10000Zagreb,Croatia,b Laboratory of Organic Chemistry,University of Zagreb,Faculty of Food Technology and Biotechnology,Pierottijeva 6,HR-10000Zagreb,Croatia,and cLaboratory of Inorganic Chemistry,Faculty of Chemistry and Chemical Technology,University of Ljubljana,PO Box 537,SI-1001Ljubljana,Slovenia Correspondence e-mail:*************Received 14April 2003Accepted 27May 2003Online 22July 2003In the title compound,[Fe(C 5H 5)(C 14H 13O)],the plane of the heterocyclic ring is almost perpendicular to the plane of the substituted cyclopentadienyl ring,and the heterocyclic ring adopts a half-chair conformation.The conformation of the nearly parallel cyclopentadienyl (Cp)rings [the dihedral angle between their planes is 2.7(1) ]is almost halfway between eclipsed and staggered,and the rings are mutually twisted by about 19.4(2) (mean value).The mean lengths of the CÐC bonds in the substituted and unsubstituted cyclopentadienylring are 1.420(2)and 1.406(3)AÊ,respectively,and the FeÐC distances range from 2.029(2)to 2.051(2)AÊ.The phenyl and unsubstituted cyclopentadienyl rings are involved in CÐH ÁÁÁ%interactions,with intermolecular H ÁÁÁcentroiddistances of 2.85and 3.14AÊfor CÐH ÁÁÁ%(Ph),and 2.88A Êfor CÐH ÁÁÁ%(Cp).In two of these interactions,the CÐH bond points towards one of the ring bonds rather than towards the ring centroid.In the crystal structure,the CÐH ÁÁÁ%interactions connect the molecules into a three-dimensional framework.CommentOptically active ferrocene derivatives are widely employed as chiral ligands in asymmetric reactions,and there is continuing interest in the development of ef®cient procedures for the preparation of these derivatives in enantiopure forms (Gonsalves &Chen,1995;Bolm et al.,1998;Pioda &Togni,1998;Perea et al.,1999).Ferrocene derivatives exhibiting centro-and planar chirality are very convenient substrates forbiotransformations (KoÈllner et al.,1998;Richards &Locke,1998;Schwink &Knochel,1998;Patti &Nicolosi,1999;akovicÂet al.,2003).In the course of our research on enzyme-catalyzed resolution of centrochiral ferrocene compounds,racemic 2-( -hydroxyferrocenyl)benzenethanol and 1-ferro-cenylisochromane,(I),were prepared by reduction of methyl2-(ferrocenoyl)benzeneacetate ( akovicÂ,2000).The molecular structure of (I)is the ®rst reported structure to contain an isochromanyl group attached to the ferrocenyl moiety (Fig.1).Moreover,the Cambridge Structural Database (Allen,2002)lists only three structures containing an iso-chromanyl group at all (Yamato et al.,1984;Unterhalt et al.,1994;Eikawa et al.,1999).The heterocyclic six-membered ringActa Crystallographica Section CCrystal Structure CommunicationsISSN0108-2701Figure 2Part of the crystal structure of (I),showing the formation of (010)sheets built from C14ÐH14A ÁÁÁCg 1i and C18ÐH18ÁÁÁCg 2ii interactions (Cg 1and Cg 2are the centroids of rings C12/C13/C16±C19and C6±C10,respectively).CÐH ÁÁÁ%interactions are indicated by dashed lines.[Symmetry codes:(i)x ,12Ày ,z À12;(ii)1+x ,y ,1+z.]Figure 1A view of (I),with the atom-numbering scheme.Displacement ellipsoids for non-H atoms are drawn at the 20%probability level.1Part XXXVIII:Cetina et al.(2003).adopts a distorted half-chair conformation,in which atoms O1and C15are 0.426(1)and À0.348(2)AÊfrom the plane of the other ring atoms (C11±C14);the C11ÐC12ÐC13ÐC14torsion angle is 2.4(2) .The bond lengths in the heterocyclic and fused phenyl rings (Table 1)mostly agree with the equivalent bond lengths in the structures of 1,1H -oxybis(iso-chromane)(Eikawa et al.,1999)and (S )-1-(phenyl)ethyl-ammonium (S )-isochromane-1-carboxylate (Unterhalt et al.,1994).The exception is the C12ÐC13bond,which is shorter($0.04AÊ)in the latter structure.Heterocyclic ring atoms O1,C11and C15and cyclopentadienyl (Cp)ring atom C1lie in the same plane,the C15ÐO1ÐC11ÐC1torsion angle being 178.95(14) .The dihedral angle between the mean plane of these four atoms and the C1±C5Cp ring is 47.8(1) .Furthermore,the plane of the heterocyclic ring is almost perpendicular to the plane of the C1±C5ring and is parallel to the plane of the fused phenyl ring.The corresponding dihedral angles are 87.3(1)and 4.0(1) .The exocyclic C2ÐC1ÐC11bond angle is larger than the C5ÐC1ÐC11angle (Table 1).The Cp rings are planar and almost parallel to each other [the dihedral angle between their planes is 2.7(1) ],and the FeÐC distances are in the range2.034(2)±2.051(2)AÊfor the substituted (C1±C5)and 2.029(2)±2.049(2)AÊfor the unsubstituted (C6±C10)ring,the average values being 2.042(2)and 2.038(2)AÊ,respectively.The CÐC bonds are slightly longer in the substituted ring than in the unsubstituted ring [1.410(3)±1.429(2)versus 1.397(3)±1.414(3)AÊ],and the bond angles in both rings range from 107.52(15)to 108.33(18) .The geometry of the ferrocenyl moiety agrees well with the structures of ferrocene (Seiler &Dunitz,1979)and of theferrocene derivatives we have reported previously (Cetina et al.,2002,2003).The main conformational difference was observed in the orientation of the Cp rings.In (I),the rings are twisted from an eclipsed conformation by 19.4(2) (mean value).The values of the corresponding CÐCg 3ÐCg 2ÐC pseudo-torsion angles (Cg 3and Cg 2are the centroids of the C1±C5and C6±C10rings,respectively),de®ned by joining two eclipsing Cp C atoms through the ring centroids,range from 19.0(2)to 19.7(2) .The conformation is almost exactly halfway between eclipsed and staggered,as demonstrated by the C1ÐCg 3ÐCg 2ÐC9torsion angle of 163.4(1) .This angle would be 180 for a staggered conformation and 144 for a fully eclipsed conformation.The centroids of the Cp rings are almost equidistant from the Fe atom;the FeÐCg 3and FeÐCg 2distances are 1.647(1)and 1.650(1)AÊ,respectively,while the Cg 3ÐFeÐCg 2angle is 178.2(1) .There are a number of CÐH ÁÁÁ%interactions (Table 2and Fig.2).Atom H14A of the heterocyclic ring is positioned almost perpendicularly above the phenyl-ring centroid (Cg 1)of the adjacent molecule.The six relevant H ÁÁÁC distances fallin the narrow range 3.06±3.28AÊ,and the H ÁÁÁCg i distance is signi®cantly shorter than any of the H ÁÁÁC distances[symmetry code:(i)x ,12Ày ,z À12;Table 2].The CÐH ÁÁÁ%interaction between phenyl atom H18and the unsubstituted Cp ring exhibits a completely different geometry.The H18ÁÁÁC7ii distance is shorter than the H ÁÁÁCg ii distance [symmetry code:(ii)1+x ,y ,1+z ].The second shortest H ÁÁÁC contact is that to atom C6,and the CÐH bond points towards the C6ÐC7bond of the Cp ring rather than towards the ring centroid (Cg 2).Similarly,the longest interaction,C5ÐH5ÁÁÁCg 1iii [symmetry code:(iii)1Àx ,Ày ,2Àz ],points towards the C12ÐC13bond.Both the H5ÁÁÁC12iii and the H5ÁÁÁC13iii contacts are shorter than the H ÁÁÁCg iii distance.The molecules linked by these CÐH ÁÁÁ%interactions build a three-dimensional framework (Fig.3).ExperimentalNaBH 4(253mg,6.7mmol)was added gradually to a solution of methyl 2-(ferrocenoyl)benzeneacetate (326mg,0.9mmol)in a mixture of EtOH and Et 2O (1:1v /v ;5ml).The mixture was re¯uxed for 2h and worked up in the usual manner.Separation by preparative thin-layer chromatography on silica gel (Merck,Kieselgel 60HF 254)yielded 2-( -hydroxyferrocenyl)benzeneethanol (237mg;yield 78%)and orange crystals of 1-ferrocenylisochromane (57mg;yield 20%;m.p.365±366K).Single crystals of the title compound were obtained by slow evaporation from a cyclohexane solution at room tempera-ture.IR (CH 2Cl 2,cm À1):)3081(w )and 3020(w )(CÐH,ferrocene),2942(m )(CÐH,aliphatic),1278(m )(CÐOÐC);1H NMR (DMSO,p.p.m.): 7.18(d ,1H,H16),7.12(d ,1H,H17),7.14(d ,1H,H18),7.16(d ,1H,H19),4.23(s ,5H,unsubstituted ferrocene ring),4.13±4.20(m ,4H,substituted ferrocene ring),3.97(m ,1H,H15A ),3.77(m ,1H,H15B ),2.78(m ,2H,H14),5.58(s ,1H,H11);13C NMR (DMSO,p.p.m.): 137.29(C12),132.91(C13),128.5(C17),126.25(C18),125.98(C16),125.36(C19),90.21(C1),73.63(C11),68.62(unsub-stituted ferrocene ring),68.56±66.31(substituted ferrocene ring),61.55(C15),27.99(C14).Acta Cryst.(2003).C 59,m328±m330Mario Cetina et al.[Fe(C 5H 5)(C 14H 13O)]m329metal-organic compoundsFigure 3Part of the crystal structure of (I),showing the cyclic motif generated by the C5ÐH5ÁÁÁCg 1iii interaction (Cg 1is the centroid of ring C12/C13/C16±C19),which links the (010)sheets into a three-dimensional framework.CÐH ÁÁÁ%interactions are indicated by dashed lines,and the unit-cell box has been omitted for clarity.[Symmetry code:(iii)1Àx ,Ày ,2Àz .]metal-organic compoundsm330Mario Cetina et al.[Fe(C 5H 5)(C 14H 13O)]Acta Cryst.(2003).C 59,m328±m330Crystal data[Fe(C 5H 5)(C 14H 13O)]M r =318.18Monoclinic,P 21a ca =11.5053(2)A Êb =18.5095(3)A Êc =7.1941(1)AÊ =106.933(1)V =1465.62(4)AÊ3Z =4D x =1.442Mg m À3Mo K radiationCell parameters from 3411re¯ections =2.6±27.5 "=1.02mm À1T =293(2)K Prism,orange0.80Â0.40Â0.15mm Data collectionNonius KappaCCD area-detector diffractometer 9and 3scansAbsorption correction:multi-scan (DENZO±SMN ;Otwinowski &Minor,1997)T min =0.630,T max =0.85716885measured re¯ections3334independent re¯ections 2662re¯ections with I >2'(I )R int =0.064 max =27.4 h =À14314k =À23323l =À939Re®nementRe®nement on F 2R [F 2>2'(F 2)]=0.030wR (F 2)=0.076S =1.033334re¯ections 190parametersH-atom parameters constrainedw =1/['2(F 2o )+(0.0341P )2+0.3545P ]where P =(F 2o +2F 2c )/3(Á/')max =0.001Á&max =0.25e A ÊÀ3Á&min =À0.23e AÊÀ3All H atoms were included in calculated positions as riding atoms,with SHELXL 97(Sheldrick,1997)defaults viz.CÐH =0.93AÊfor aromatic H atoms,0.98AÊfor methine H atoms,and 0.97A Êfor methylene H atoms.For all H atoms,the isotropic displacement parameters were set at 1.2times the equivalent anisotropic displacement parameters of the attached non-H atoms.Data collection:COLLECT (Nonius,2000);cell re®nement:DENZO±SMN (Otwinowski &Minor,1997);data reduction:DENZO±SMN ;program(s)used to solve structure:SHELXS 97(Sheldrick,1997);program(s)used to re®ne structure:SHELXL 97(Sheldrick,1997);molecular graphics:PLATON (Spek,2003);soft-ware used to prepare material for publication:SHELXL 97.The re¯ection data were collected at the Faculty of Chem-istry and Chemical Technology,University of Ljubljana,Slovenia.We acknowledge with thanks the ®nancial contri-bution of the Ministry of Education,Science and Sport of the Republic of Slovenia (grant Nos.X-2000and PS-511-103),which made the purchase of the apparatus possible.Supplementary data for this paper are available from the IUCr electronic archives (Reference:GD1251).Services for accessing these data are described at the back of the journal.ReferencesAllen,F.H.(2002).Acta Cryst.B 58,380±388.Bolm,C.,MunÄiz-Ferna Ândez,K.,Seger,A.,Raabe,G.&Gunther,K.(1998).Chem.63,7860±7867.Cetina,M.,Hergold-BrundicÂ,A.,Nagl,A.,Jukic Â,M.&Rapic Â,V .(2003).Struct.Chem.14,289±293.Cetina,M.,MrvosÏ-Sermek,D.,Jukic Â,M.&Rapic Â,V .(2002).Acta Cryst.E 58,m676±m678.akovicÂ,S.(2000).PhD thesis,University of Zagreb,Croatia. akovicÂ,S.,Lapic Â,J.&Rapic Â,V .(2003).Biocatal.Biotransform.In the press.Eikawa,M.,Sakaguchi,S.&Ishii,Y.(1999).Chem.64,4676±4679.Gonsalves,K.E.&Chen,X.(1995).Ferrocenes ,edited by A.Togni &T.Hayashi,ch.10,pp.497±527.Weinheim:VCH.KoÈllner,C.,Pugin,B.&Togni,A.(1998).J.Am.Chem.Soc.120,10274±10275.Nonius (2000).COLLECT.Nonius BV ,Delft,The Netherlands.Otwinowski,Z.&Minor,W.(1997).Methods in Enzymology ,Vol.276,Macromolecular Crystallography ,Part A,edited by C.W.Carter Jr &R.M.Sweet,pp.307±326.New York:Academic Press.Patti,A.&Nicolosi,G.(1999).Tetrahedron :Asymmetry ,10,2651±2654.Perea,J.J.A.,Lotz,M.&Knochel,P .(1999).Tetrahedron :Asymmetry ,10,375±384.Pioda,G.&Togni,A.(1998).Tetrahedron :Asymmetry ,9,3903±3910.Richards,C.J.&Locke,A.(1998).Tetrahedron :Asymmetry ,9,2377±2407.Schwink,L.&Knochel,P .(1998).Chem.Eur.J.4,950±968.Seiler,P .&Dunitz,J.D.(1979).Acta Cryst.B 35,2020±2032.Sheldrick,G.M.(1997).SHELXS 97and SHELXL 97.University ofGoÈttingen,Germany.Spek,A.L.(2003).J.Appl.Cryst.36,7±13.Unterhalt,B.,Krebs,B.,Lage,M.&Nocon,B.(1994).Arch.Pharm.327,799±804.Yamato,M.,Hashigaki,K.,Kokubu,N.&Nakato,Y.(1984).J.Chem.Soc.Perkin Trans.1,pp.1301±1304.Table 2Hydrogen-bonding geometry (AÊ, ).Cg 1and Cg 2are the centroids of rings C12/C13/C16±C19and C6±C10,respectively.D ÐH ÁÁÁA D ÐH H ÁÁÁA D ÁÁÁA D ÐH ÁÁÁA C14ÐH14A ÁÁÁCg 1i 0.97 2.85 3.627(2)138C18ÐH18ÁÁÁCg 2ii 0.93 2.88 3.660(2)142C18ÐH18ÁÁÁC7ii 0.93 2.86 3.760(3)163C18ÐH18ÁÁÁC6ii 0.93 3.03 3.874(3)151C5ÐH5ÁÁÁCg 1iii 0.93 3.14 3.984(2)152C5ÐH5ÁÁÁC12iii 0.93 2.98 3.840(2)154C5ÐH5ÁÁÁC13iii0.933.023.949(2)177Symmetry codes:(i)x Y 12Ày Y z À12;(ii)1 x Y y Y 1 z ;(iii)1Àx Y Ày Y 2Àz .Table 1Selected geometric parameters (AÊ, ).O1ÐC111.4236(19)O1ÐC15 1.432(2)C1ÐC11 1.503(2)C11ÐC12 1.523(2)C12ÐC16 1.388(2)C12ÐC13 1.397(2)C13ÐC19 1.392(3)C13ÐC14 1.504(3)C14ÐC15 1.501(3)C16ÐC17 1.384(3)C17ÐC18 1.380(3)C18ÐC19 1.379(3)C11ÐO1ÐC15110.39(13)C2ÐC1ÐC11127.61(14)C5ÐC1ÐC11124.78(14)O1ÐC11ÐC1109.37(13)O1ÐC11ÐC12111.64(13)C1ÐC11ÐC12112.14(13)C13ÐC12ÐC11119.77(14)C12ÐC13ÐC14120.38(16)C15ÐC14ÐC13111.24(15)O1ÐC15ÐC14110.04(15)。
211262186_Cu-MOF_材料的合成及其对有机小分子的荧光识别
第52卷第5期 辽 宁 化 工 Vol.52，No. 5 2023年5月 Liaoning Chemical Industry May，2023基金项目：① 2021年贵州省大学生创新创业训练计划项目（国家级）（项目编号：202110667029） ；②2021年贵州省大学生创新创业训练计划 项目（省级）（项目编号：202110667005）；③贵州省教育厅2021年度市（州）普通本科高校青年科技人才成长项目（项目编号：黔 教合KY 字[2022]036号）。
收稿日期： 2022-09-29Cu -MOF 材料的合成 及其对有机小分子的荧光识别文勇武，江创，张玉蝶，熊琴，赵永婷*（安顺学院， 贵州 安顺 561000）摘 要：通过水热法合成了一例Cu-MOF 材料（化合物1）。
单晶衍射分析表明化合物1属于单斜晶系，空间群为P21/c ，晶胞参数a = 7.309 6，b =10.917 4，c =14.114 5，α=90，β=91.497，γ=90 。
对化合物1进行荧光性能研究，荧光结果分析表明，在260 nm 的激发波长下，化合物1在390 nm 处有强的荧光发射峰。
并研究了化合物1对不同有机溶剂分子的荧光特性。
通过荧光光谱测试表明，化合物1在乙醇溶液中表现出荧光猝灭现象，对乙醇溶剂具有良好的荧光识别性能。
关 键 词：Cu-MOF 材料；有机溶剂；荧光；识别中图分类号：TQ201 文献标识码： A 文章编号： 1004-0935（2023）05-0627-04金属有机框架材料(MOFs ），又称为配位聚合物材料，是由金属离子或者金属团簇与有机配体通过配位键自组装连接而成的一维、二维或三维结 构[1]。
金属中心的配位模式、金属半径大小以及配体的配位齿的数目、配位点间的间距、配体的给体基团性质等都会对整个自组装过程起决定性作用。
合成MOFs 材料的方法主要有水热法、溶剂热法、微波合成法、电化学法和其他方法等[2-4]，水热合成至今已有100多年历史，目前已经发展成金属有机框架材料合成的主要途径之一。
Acta Cryst. (2013). C69, 1017–1021
One-dimensional Cu I and Ag I ladder-like coordination polymers supported by 2-ethyl-1-(pyridin-3-ylmethyl)-1H -benzimidazoleLiu-cheng Gui,*Guang-ming Liang,Hua-hong Zou and Zhong HouSchool of Chemistry and Chemical Engineering,Guangxi Normal University,Guilin 541004,People’s Republic of ChinaCorrespondence e-mail:guiliucheng2000@ Received 25May 2013Accepted 19July 2013The title complexes,poly[[bis[ 2-2-ethyl-1-(pyridin-3-ylmeth-yl)-1H -benzimidazole- 2N 1:N 3]copper(I)]tetrafluoroborate acetonitrile monosolvate],{[Cu(C 15H 15N 3)2]BF 4ÁCH 3CN}n ,(I),and poly[[bis[ 2-2-ethyl-1-(pyridin-3-ylmethyl)-1H -benz-imidazole- 2N 1:N 3]silver(I)]perchlorate methanol monosol-vate],{[Ag(C 15H 15N 3)2]ClO 4ÁCH 3OH}n ,(II),are isostructural and exhibit one-dimensional ladder-like structures in which each asymmetric unit contains one metal ion (Cu +or Ag +),two 2-ethyl-1-(pyridin-3-ylmethyl)-1H -benzimidazole (bep)ligands,one counter-anion (tetrafluoroborate or perchlorate)and one interstitial molecule (acetonitrile or methanol).Each metal ion exhibits a distorted tetrahedral coordination geometry consisting of two pyridyl and two benzimidazole N atoms from four distinct ligands.Two metal ions are linked by two bep ligands to form a centrosymmetric 18-membered M 2(bep)2metallacycle,while adjacent M 2(bep)2metallacycles are further interlinked by another two bep ligands resulting in a ladder-like array.In the extended structure,four adjacent ladder-like arrays are connected together through C—H ÁÁÁF,O—H ÁÁÁO and C—H ÁÁÁO hydrogen bonds between bep ligands,solvent molecules and counter-anions into a three-dimensional supramolecular structure.Keywords:crystal structure;inorganic–organic coordination polymers;2-ethyl-1-(pyridin-3-ylmethyl)benzimidazole ligand;crystal engineering.1.IntroductionCurrently,the rational design and synthesis of inorganic–organic coordination polymers have attracted considerable attention due to the intriguing variety of architectures and topologies that can be produced,and the potential applica-et al.,2007;Murray et al.,2009;Zhang,Liu et al.,2010;Zhang,Zhang et al.,2013).Many factors,such as the metal centres (as nodes),organic linkers (as building blocks),solvent molecules,temperature,templates,counter-anions etc .,can affect the final architectures (Tong et al.,1998;Ferey et al.,2005;Bradshaw et al.,2005;Uemura et al.,2006;Zhang,Wang et al.,2010).In particular,the structure of the ligand and the coordination mode of the metal ion play key roles in determining the nature of the coordination polymer (Liu et al.,2007;Lee et al.,2008;Zheng et al.,2009).There has been much interest and progress recently in the crystal engineering of supramolecular architectures organized and sustained by means of bis-heterocyclic chelating or brid-ging ligands with pyridine,pyrazine,imidazole and diazoles;and 4,40-bipyridine and its derivatives have been the most frequently used bridging ligands for constructing interesting grid or chain-like coordination polymers (Hartshorn et al.,1998;Li et al.,2007;Zhai et al.,2011).Recently,pyridyl/benzimidazolyl-based ligands with a freely rotatable methyl-ene (–CH 2–)juncture between the pyridyl ring and the benzimidazole moiety have attracted considerable attention for two main reasons:(i)they possess flexibility owing to the presence of the methylene (–CH 2–)spacer;(ii)they can act as 2-bridging ligands via the pyridyl and benzimidazole N atoms.In previous studies,N -(pyridin-2-ylmethyl)-1H -benzi-midazole (2-pb-m),N -(pyridin-3-ylmethyl)-1H -benzimidazole (3-pb-m)and N -(pyridin-4-ylmethyl)-1H -benzimidazole (4-pb-m)have been used to create one-dimensional double-helical chains,and two-and three-dimensional networks with d 10metals (Wang et al.,2009;Huang et al.,2006).To extend the study of these types of ligands,an ethyl group was introduced into the 2-position of the benzimidazole system,giving the new ligand 2-ethyl-1-(pyridin-3-ylmethyl)-1H -benzimidazole (bep),which is expected to produce inter-esting structures mediated by the steric and electronic effects of the ethyl group.In this study,two isostructural compounds,{[Cu(bep)2]BF 4ÁCH 3CN}n ,(I),and {[Ag(bep)2]ClO 4ÁCH 3-OH}n ,(II),were obtained by the reaction of bep and [Cu(CH 3CN)4]BF 4or AgClO 4.These isostructural complexes metal-organic compoundsActa Crystallographica Section CCrystal Structure CommunicationsISSN0108-27012.Experimental2.1.Synthesis and crystallizationBep was synthesized according to the method reported by Huang et al.(2006).For the preparation of (I),a solution of [Cu(CH 3CN)4]BF 4(0.05mmol)in a mixture of CH 3CN (3ml)and N ,N -dimethylformamide (DMF,3ml)was added to bep (0.1mmol).A yellow solution formed and was filtered.Diethyl ether was diffused slowly into the solution and,after several days,yellow block-shaped crystals suitable for X-ray diffrac-tion analysis had formed (yield 60%).Elemental analysis calculated for C 32H 33BCuF 4N 7:C 57.71,H 4.99,N 14.72%;found:C 57.48,H 5.12,N 14.34%.For the preparation of (II),a solution of AgClO 4(0.05mmol)in a mixture of CH 3OH (3ml)and DMF (3ml)was added to bep (0.1mmol).A yellow solution formed and was filtered.Diethyl ether was diffused slowly into the solution and,after several days,yellow block-shaped crystals suitable for X-ray diffraction analysis had formed (yield 80%).Elemental analysis calculated for C 31H 34AgClN 6O 5:C 52.15,H 4.80,N 11.77%;found:C 52.01,H 4.96,N 11.46%.2.2.RefinementCrystal data,data collection and structure refinement details are summarized in Table 1.In both structures,all C-bound H atoms were placed in idealized positions,withC—H =0.93A˚and U iso (H)=1.2U eq (C)for aromatic H atoms,˚In order to make the refinement of the acetonitrile solvent molecules in (I)and the methanol solvent molecules in (II)fully anisotropic,all their C,N and O atoms were subjected to a ‘rigid bond’restraint (DELU instruction in SHELXL97;Sheldrick,2008),i.e.the mean-square displacements in the direction of the corresponding bonds were restrained to beequal within an effective standard uncertainty of 0.005A˚2.In addition,within this same set of atoms,those closer than 1.7A˚were restrained with an effective standard uncertainty ofmetal-organic compoundsTable 1Experimental details.(I)(II)Crystal dataChemical formula [Cu(C 15H 15N 3)2]BF 4ÁC 2H 3N[Ag(C 15H 15N 3)2]ClO 4ÁCH 4O M r666.00713.96Crystal system,space group Triclinic,P 1Triclinic,P 1Temperature (K)298298a ,b ,c (A˚)9.3674(4),12.5367(6),13.3150(7)9.560(7),12.946(10),13.849(11) , , ( )89.912(2),72.786(2),84.599(1)90.163(10),108.773(9),95.518(9)V (A ˚3)1486.42(12)1614(2)Z22Radiation type Mo K Mo K (mm À1)0.800.76Crystal size (mm)0.68Â0.21Â0.150.60Â0.20Â0.18Data collection DiffractometerBruker SMART CCD area-detector diffractometerBruker SMART CCD area-detector diffractometerAbsorption correction Multi-scan (SADABS ;Bruker,2001)Multi-scan (SADABS ;Bruker,2001)T min ,T max0.614,0.8900.850,0.860No.of measured,independent and observed [I >2 (I )]reflections 14603,6748,600410939,7140,5396R int0.0200.018(sin / )max (A˚À1)0.6490.670RefinementR [F 2>2 (F 2)],wR (F 2),S 0.047,0.141,1.090.044,0.118,1.02No.of reflections 67487140No.of parameters 408400No.of restraints 209H-atom treatmentH-atom parameters constrained H-atom parameters constrained Á max ,Á min (e A˚À3) 2.18,À0.910.78,À0.51Computer programs:SMART (Bruker,2001),SAINT (Bruker,2007),SHELXS97(Sheldrick,2008),SHELXL97(Sheldrick,2008)and SHELXTL (Sheldrick,2008).Figure 1A view of (I),showing the atom-labelling scheme.Displacement ellipsoids are drawn at the 30%probability level.H atoms are shown as small spheres of arbitrary radii and have been omitted from symmetry-0.005A˚2to have the same U ij components(SIMU instruc-tion).The refinement of the H atoms of the acetonitrile solvent molecules in(II)required the inclusion of inter-molecular restraints to avoid convergence to unreasonable intermolecular HÁÁÁH distances.The intermolecular HÁÁÁH shortest contact distances were restrained to2.30A˚.Bond distances involving non-H atoms in these groups were also subjected to distance restraints.3.Results and discussionAs compounds(I)and(II)are isostructural,only the structure of(I)is described in detail here.The asymmetric unit of(I) contains one Cu I atom,two coordinated bep ligands,one tetrafluoroborate counter-anion and one lattice acetonitrile molecule(Fig.1).The Cu I centre adopts a distorted tetra-hedral coordination geometry consisting of two pyridyl(py)N atoms[N6i and N3ii;symmetry codes:(i)Àx+1,Ày,Àz+1; (ii)x+1,y,z]and two benzimidazole(Bm)N atoms(N1and N4),which are from four distinct ligands.The Cu—N Bm bond lengths[2.018(2)and2.041(2)A˚]are distinctly shorter than those of Cu—N py[2.108(2)and 2.155(2)A˚]due to the benzimidazole group being more electron-rich,and hence a stronger donor,than the pyridyl group.The same results have been observed by others(Su et al.,1999).The bond angles around each Cu I centre(Table2)are within the expected range for similar complexes(Su et al.,1999).In(II),the Ag—N Bm[2.230(3)and2.257(3)A˚]and Ag—N py[2.397(3) and2.443(3)A˚]bond lengths are all longer than the Cu—N bonds in(I)due to the Ag+radius being larger than that of Cu+(Huang et al.,2006).Two metal ions are bridged by two 2-bep ligands,forming an18-membered M2(bep)2metallacycle with an MÁÁÁM separation of7.933(1)A˚for(I)and8.167(5)A˚for(II) (Fig.2).C—HÁÁÁ interactions between ethyl H atoms of one ligand and the benzimidazole system of another molecule further stabilize the metallacycle[C—HÁÁÁ (centroid)= 3.086A˚for(I),with atom C24as donor,via atom H24C,to the C16A–C21A ring at(Àx+1,Ày,Àz+1),and3.303A˚for(II), with atom C24as donor,via atom H24B,to the C16A–C21A ring at(Àx,Ày,Àz+1)].The metallacycles can be viewed as the rungs of the ladder,which are further connected by two bep ligands to form one-dimensional ladder-like arrays,with MÁÁÁM separations of9.368(1)A˚for(I)and9.560(7)A˚for (II).In contrast with other analogues,the title compounds exhibit one-dimensional ladder-like coordination polymers with metallacycle units,which may be the result of two factors: (i)the ligand possessingflexibility owing to the presence of a methylene(–CH2–)spacer between the pyridyl ring and the benzimidazole moiety;(ii)the steric and electronic effect of the ethyl group introduced into the2-position of benzimida-zole.Thus,the present work once again emphasizes themetal-organic compoundsFigure2(a)The one-dimensional ladder-like chain of(I)and(II),(b)the18-membered M2(bep)2metallacycle and(c)a schematic view of the one-dimensional ladder-like chain.The Cu atoms and organic linker ligands are represented by red balls and curved lines,respectively.Table2Selected geometric parameters(A˚, )for(I).Cu1—N1 2.018(2)Cu1—N6i 2.108(2) Cu1—N4 2.041(2)Cu1—N3ii 2.155(2) N1—Cu1—N4126.94(9)N1—Cu1—N3ii118.24(8) N1—Cu1—N6i101.41(8)N4—Cu1—N3ii99.80(9) N4—Cu1—N6i104.97(9)N6i—Cu1—N3ii102.48(9)Table3Hydrogen-bond geometry(A˚, )for(I).D—HÁÁÁA D—H HÁÁÁA DÁÁÁA D—HÁÁÁA C10—H10AÁÁÁF2iii0.97 2.55 3.505(4)169C10—H10BÁÁÁF40.97 2.39 3.353(3)175C19—H19AÁÁÁF3iv0.93 2.53 3.412(3)158important role played by both the metal centres and organic linkers on thefinal structures of coordination complexes.In the crystal packing,four adjacent ladder-like arrays are connected through C—HÁÁÁF,O—HÁÁÁO and C—HÁÁÁO sional supramolecular structure.In(I),the tetrafluoroborate anion connects four adjacent ladder-like arrays through C19—H19AÁÁÁF3,C10—H10AÁÁÁF2and C10—H10BÁÁÁF4hydro-gen bonds(Table3),forming the three-dimensional super-molecular structure(Fig.3a).In(II),the perchlorate anion acts in the same manner through C10—H10AÁÁÁO3,C23—H23AÁÁÁO4,O5—H5BÁÁÁO1and C31—H31CÁÁÁO3hydrogen bonds(Table5and Fig.3b).This work is supported by National NSF of China(No. 21201045)and NSF of Guangxi Province(No.2013-GXNSFBA019039).Supplementary data for this paper are available from the IUCr electronic archives(Reference:WQ3040).Services for accessing these data are 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C69, 1017-1021 [doi:10.1107/S0108270113019963]One-dimensional Cu I and Ag I ladder-like coordination polymers supported by 2-ethyl-1-(pyridin-3-ylmethyl)-1H-benzimidazoleLiu-cheng Gui, Guang-ming Liang, Hua-hong Zou and Zhong HouComputing detailsFor both compounds, data collection: SMART (Bruker, 2001); cell refinement: SAINT (Bruker, 2007); data reduction: SAINT (Bruker, 2007); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: SHELXTL97 (Sheldrick, 2008); software used to prepare material for publication: SHELXTL97 (Sheldrick, 2008).(1) Poly[[bis[µ2-2-ethyl-1-(pyridin-3-ylmethyl)-1H-benzimidazole-κ2N1:N3]copper(I)] tetrafluoroborate acetonitrile monosolvate]Crystal data[Cu(C15H15N3)2]BF4·C2H3N M r = 666.00Triclinic, P1Hall symbol: -P 1a = 9.3674 (4) Åb = 12.5367 (6) Åc = 13.3150 (7) Åα = 89.912 (2)°β = 72.786 (2)°γ = 84.599 (1)°V = 1486.42 (12) Å3Z = 2F(000) = 688D x = 1.488 Mg m−3Mo Kα radiation, λ = 0.71073 Åθ = 2.2–25.0°µ = 0.80 mm−1T = 298 KBlock, yellow0.68 × 0.21 × 0.15 mmData collectionBruker SMART CCD area-detector diffractometerRadiation source: fine-focus sealed tube Graphite monochromatorω scansAbsorption correction: multi-scan (SADABS; Bruker, 2001)T min = 0.614, T max = 0.89014603 measured reflections 6748 independent reflections 6004 reflections with I > 2σ(I) R int = 0.020θmax = 27.5°, θmin = 3.2°h = −11→12k = −16→16l = −17→17RefinementRefinement on F2Least-squares matrix: full R[F2 > 2σ(F2)] = 0.047 wR(F2) = 0.141S = 1.096748 reflections408 parameters 20 restraintsPrimary atom site location: structure-invariant direct methodsSecondary atom site location: difference Fourier mapHydrogen site location: inferred from neighbouring sitesH-atom parameters constrainedw = 1/[σ2(F o2) + (0.0762P)2 + 1.632P] where P = (F o2 + 2F c2)/3(Δ/σ)max = 0.001Δρmax = 2.17 e Å−3Δρmin = −0.91 e Å−3Special detailsGeometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes. Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2)x y z U iso*/U eqCu10.42937 (3)0.24036 (2)0.32103 (2)0.02427 (12)N10.2425 (2)0.25010 (17)0.27419 (17)0.0219 (4)N20.0736 (2)0.30988 (17)0.19341 (17)0.0224 (4)N3−0.4284 (2)0.36926 (18)0.28324 (19)0.0264 (5)N40.4437 (2)0.20740 (18)0.46810 (17)0.0236 (4)N50.3778 (2)0.18863 (17)0.64224 (17)0.0219 (4)C10.1811 (3)0.1626 (2)0.24431 (19)0.0203 (5)C20.2104 (3)0.0532 (2)0.2570 (2)0.0237 (5)H2A0.27810.02790.29250.028*C30.1360 (3)−0.0165 (2)0.2153 (2)0.0262 (5)H3A0.1537−0.08980.22310.031*C40.0341 (3)0.0211 (2)0.1613 (2)0.0258 (5)H4A−0.0128−0.02810.13300.031*C50.0017 (3)0.1294 (2)0.1492 (2)0.0242 (5)H5A−0.06640.15450.11400.029*C60.0762 (3)0.1991 (2)0.19250 (19)0.0211 (5)C70.1748 (3)0.3359 (2)0.2426 (2)0.0218 (5)C80.2027 (3)0.4474 (2)0.2649 (2)0.0287 (6)H8A0.16130.49690.22230.034*H8B0.30990.45270.24630.034*C90.1310 (4)0.4775 (3)0.3803 (3)0.0410 (7)H9A0.15510.54770.39420.061*H9B0.16850.42650.42250.061*H9C0.02400.47750.39740.061*C10−0.0160 (3)0.3819 (2)0.1425 (2)0.0258 (5)H10A−0.02280.34660.07950.031*H10B0.03440.44610.12140.031*C11−0.1724 (3)0.4132 (2)0.2146 (2)0.0246 (5)C12−0.2054 (3)0.5024 (2)0.2813 (3)0.0348 (6)H12A−0.13170.54750.28060.042*C13−0.3498 (3)0.5242 (2)0.3495 (3)0.0390 (7)H13A−0.37420.58420.39450.047*C14−0.4565 (3)0.4553 (2)0.3491 (3)0.0334 (6)H14A−0.55190.46900.39660.040*C15−0.2892 (3)0.3507 (2)0.2169 (2)0.0241 (5)H15A−0.26910.29270.16960.029*C160.5692 (3)0.2153 (2)0.5031 (2)0.0224 (5)C170.7172 (3)0.2302 (2)0.4468 (2)0.0292 (6)H17A0.74710.23420.37390.035*C180.8175 (3)0.2389 (2)0.5038 (2)0.0316 (6)H18A0.91670.24900.46840.038*C190.7736 (3)0.2327 (2)0.6133 (2)0.0305 (6)H19A0.84370.24080.64900.037*C200.6278 (3)0.2147 (2)0.6704 (2)0.0265 (5)H20A0.59860.20930.74320.032*C210.5286 (3)0.20541 (19)0.6119 (2)0.0213 (5)C220.3333 (3)0.1911 (2)0.5532 (2)0.0225 (5)C230.1791 (3)0.1729 (2)0.5521 (2)0.0287 (6)H23A0.16140.20330.48930.034*H23B0.10650.20950.61270.034*C240.1566 (3)0.0542 (3)0.5543 (2)0.0361 (7)H24A0.05740.04540.55090.054*H24B0.16870.02480.61820.054*H24C0.22940.01760.49510.054*C250.2879 (3)0.1741 (2)0.7503 (2)0.0268 (5)H25A0.18350.17390.75250.032*H25B0.29500.23450.79340.032*C260.3357 (3)0.0720 (2)0.7968 (2)0.0230 (5)C270.3125 (3)0.0668 (2)0.9045 (2)0.0325 (6)H27A0.27030.12670.94800.039*C280.3528 (4)−0.0283 (3)0.9463 (2)0.0364 (7)H28A0.3378−0.0334 1.01830.044*N70.6571 (12)0.7019 (7)−0.0088 (9)0.223 (5)C310.6053 (9)0.6234 (8)0.0375 (6)0.163 (4)C320.5185 (11)0.5398 (8)0.0993 (5)0.329 (9)H32A0.49360.55760.17290.493*H32B0.57770.47180.08460.493*H32C0.42790.53600.08020.493*B10.1334 (4)0.7004 (3)0.1088 (3)0.0328 (7)F10.2692 (3)0.7337 (2)0.1087 (2)0.0653 (7)F20.0565 (4)0.77528 (18)0.06303 (19)0.0726 (8)F30.0482 (2)0.69078 (16)0.21312 (14)0.0425 (4)F40.1548 (2)0.60215 (14)0.05601 (14)0.0417 (4)C290.4154 (3)−0.1153 (2)0.8800 (2)0.0294 (6)H29A0.4434−0.17860.90880.035*N60.4381 (2)−0.11307 (18)0.77614 (17)0.0240 (4)C300.3979 (3)−0.0203 (2)0.73583 (19)0.0216 (5)H30A0.4125−0.01790.66370.026*Atomic displacement parameters (Å2)U11U22U33U12U13U23Cu10.01949 (17)0.02608 (18)0.03104 (19)0.00154 (12)−0.01450 (13)−0.00219 (12)N10.0167 (9)0.0234 (10)0.0271 (10)0.0003 (8)−0.0096 (8)−0.0004 (8) N20.0161 (9)0.0239 (10)0.0299 (11)−0.0011 (8)−0.0115 (8)0.0022 (8)N30.0185 (10)0.0249 (11)0.0380 (12)−0.0013 (8)−0.0121 (9)0.0007 (9)N40.0146 (9)0.0292 (11)0.0289 (11)−0.0011 (8)−0.0099 (8)−0.0011 (8) N50.0154 (9)0.0236 (10)0.0273 (11)0.0013 (8)−0.0083 (8)−0.0017 (8) C10.0152 (10)0.0244 (12)0.0219 (11)−0.0006 (9)−0.0070 (9)−0.0017 (9) C20.0184 (11)0.0272 (12)0.0265 (12)0.0003 (9)−0.0091 (9)0.0022 (9)C30.0225 (12)0.0240 (12)0.0313 (13)−0.0022 (10)−0.0068 (10)0.0008 (10) C40.0201 (11)0.0290 (13)0.0295 (13)−0.0060 (10)−0.0081 (10)−0.0028 (10) C50.0171 (11)0.0315 (13)0.0255 (12)−0.0018 (10)−0.0087 (9)0.0004 (10) C60.0149 (10)0.0244 (12)0.0237 (11)0.0000 (9)−0.0059 (9)0.0017 (9)C70.0141 (10)0.0242 (12)0.0277 (12)0.0008 (9)−0.0080 (9)−0.0012 (9) C80.0227 (12)0.0249 (13)0.0428 (15)−0.0024 (10)−0.0161 (11)0.0018 (11) C90.0428 (17)0.0322 (15)0.0492 (18)0.0005 (13)−0.0168 (15)−0.0122 (13) C100.0187 (11)0.0287 (13)0.0336 (13)−0.0021 (10)−0.0133 (10)0.0078 (10) C110.0188 (11)0.0204 (11)0.0391 (14)−0.0017 (9)−0.0155 (10)0.0074 (10) C120.0233 (13)0.0239 (13)0.062 (2)−0.0019 (10)−0.0206 (13)−0.0026 (12) C130.0274 (14)0.0240 (13)0.067 (2)0.0042 (11)−0.0185 (14)−0.0142 (13) C140.0201 (12)0.0294 (14)0.0506 (17)0.0054 (10)−0.0128 (12)−0.0085 (12) C150.0188 (11)0.0237 (12)0.0334 (13)−0.0006 (9)−0.0136 (10)0.0010 (10) C160.0166 (11)0.0251 (12)0.0291 (12)−0.0006 (9)−0.0128 (10)0.0006 (9)C170.0182 (12)0.0389 (15)0.0330 (14)−0.0041 (11)−0.0112 (10)0.0081 (11) C180.0182 (12)0.0370 (15)0.0450 (16)−0.0076 (11)−0.0161 (11)0.0117 (12) C190.0247 (13)0.0316 (14)0.0442 (16)−0.0055 (11)−0.0232 (12)0.0062 (11) C200.0260 (13)0.0272 (13)0.0311 (13)−0.0010 (10)−0.0163 (11)0.0007 (10) C210.0165 (11)0.0188 (11)0.0300 (12)−0.0003 (9)−0.0097 (9)−0.0012 (9) C220.0162 (11)0.0235 (12)0.0287 (12)0.0022 (9)−0.0095 (9)−0.0034 (9) C230.0129 (11)0.0407 (15)0.0341 (14)−0.0028 (10)−0.0092 (10)−0.0014 (11) C240.0277 (14)0.0476 (18)0.0373 (15)−0.0150 (13)−0.0130 (12)−0.0007 (13) C250.0204 (12)0.0294 (13)0.0271 (13)0.0046 (10)−0.0037 (10)−0.0032 (10) C260.0146 (10)0.0285 (12)0.0242 (12)−0.0004 (9)−0.0037 (9)−0.0021 (9) C270.0305 (14)0.0385 (15)0.0249 (13)0.0033 (12)−0.0046 (11)−0.0073 (11) C280.0381 (16)0.0488 (18)0.0200 (12)−0.0009 (13)−0.0061 (11)0.0009 (11) N70.185 (8)0.191 (9)0.219 (10)−0.045 (7)0.062 (7)−0.061 (7) C310.110 (6)0.216 (9)0.097 (5)0.067 (5)0.046 (4)0.071 (5)C320.142 (9)0.268 (14)0.457 (17)0.053 (9)0.071 (12)0.198 (13)B10.0459 (19)0.0272 (15)0.0255 (15)−0.0008 (14)−0.0120 (13)0.0028 (11) F10.0552 (14)0.0650 (15)0.0721 (16)−0.0250 (12)−0.0073 (12)−0.0162 (12) F20.136 (2)0.0401 (11)0.0522 (13)0.0193 (13)−0.0523 (15)0.0049 (9)F30.0422 (10)0.0499 (11)0.0315 (9)0.0071 (8)−0.0087 (8)0.0014 (8)F40.0626 (12)0.0299 (9)0.0356 (9)−0.0032 (8)−0.0194 (9)−0.0026 (7) C290.0270 (13)0.0358 (14)0.0267 (13)−0.0018 (11)−0.0103 (11)0.0065 (11) N60.0182 (10)0.0277 (11)0.0269 (11)−0.0001 (8)−0.0087 (8)−0.0009 (8) C300.0173 (11)0.0269 (12)0.0212 (11)0.0005 (9)−0.0072 (9)−0.0011 (9) Geometric parameters (Å, º)Cu1—N1 2.018 (2)C14—H14A0.9300Cu1—N4 2.041 (2)C15—H15A0.9300Cu1—N6i 2.108 (2)C16—C21 1.394 (4)Cu1—N3ii 2.155 (2)C16—C17 1.397 (4) N1—C7 1.328 (3)C17—C18 1.383 (4) N1—C1 1.396 (3)C17—H17A0.9300 N2—C7 1.364 (3)C18—C19 1.396 (4) N2—C6 1.386 (3)C18—H18A0.9300 N2—C10 1.474 (3)C19—C20 1.392 (4) N3—C15 1.341 (3)C19—H19A0.9300 N3—C14 1.348 (4)C20—C21 1.390 (3) N3—Cu1iii 2.155 (2)C20—H20A0.9300 N4—C22 1.320 (3)C22—C23 1.487 (3) N4—C16 1.398 (3)C23—C24 1.522 (4) N5—C22 1.368 (3)C23—H23A0.9700 N5—C21 1.386 (3)C23—H23B0.9700 N5—C25 1.458 (3)C24—H24A0.9600 C1—C2 1.393 (3)C24—H24B0.9600 C1—C6 1.402 (3)C24—H24C0.9600 C2—C3 1.380 (4)C25—C26 1.509 (4) C2—H2A0.9300C25—H25A0.9700 C3—C4 1.403 (4)C25—H25B0.9700 C3—H3A0.9300C26—C27 1.387 (4) C4—C5 1.384 (4)C26—C30 1.390 (3) C4—H4A0.9300C27—C28 1.383 (4) C5—C6 1.392 (4)C27—H27A0.9300 C5—H5A0.9300C28—C29 1.374 (4) C7—C8 1.492 (4)C28—H28A0.9300 C8—C9 1.517 (4)N7—C31 1.223 (5) C8—H8A0.9700C31—C32 1.482 (5) C8—H8B0.9700C32—H32A0.9600 C9—H9A0.9600C32—H32B0.9600 C9—H9B0.9600C32—H32C0.9600 C9—H9C0.9600B1—F1 1.375 (4) C10—C11 1.511 (4)B1—F2 1.379 (4) C10—H10A0.9700B1—F4 1.387 (4) C10—H10B0.9700B1—F3 1.394 (4) C11—C12 1.383 (4)C29—N6 1.337 (3) C11—C15 1.398 (3)C29—H29A0.9300 C12—C13 1.390 (4)N6—C30 1.348 (3) C12—H12A0.9300N6—Cu1i 2.108 (2) C13—C14 1.382 (4)C30—H30A0.9300 C13—H13A0.9300N1—Cu1—N4126.94 (9)N3—C15—H15A118.1N1—Cu1—N6i101.41 (8)C11—C15—H15A118.1N4—Cu1—N6i104.97 (9)C21—C16—C17120.2 (2) N1—Cu1—N3ii118.24 (8)C21—C16—N4109.5 (2) N4—Cu1—N3ii99.80 (9)C17—C16—N4130.3 (2) N6i—Cu1—N3ii102.48 (9)C18—C17—C16117.4 (3) C7—N1—C1105.5 (2)C18—C17—H17A121.3C7—N1—Cu1128.08 (17)C16—C17—H17A121.3C1—N1—Cu1124.81 (16)C17—C18—C19121.7 (2) C7—N2—C6107.2 (2)C17—C18—H18A119.2C7—N2—C10128.2 (2)C19—C18—H18A119.2C6—N2—C10124.4 (2)C20—C19—C18121.8 (2) C15—N3—C14117.2 (2)C20—C19—H19A119.1C15—N3—Cu1iii119.66 (18)C18—C19—H19A119.1C14—N3—Cu1iii119.59 (19)C21—C20—C19115.9 (2) C22—N4—C16105.4 (2)C21—C20—H20A122.1C22—N4—Cu1127.69 (17)C19—C20—H20A122.1C16—N4—Cu1126.17 (17)N5—C21—C20131.3 (2) C22—N5—C21107.0 (2)N5—C21—C16105.6 (2) C22—N5—C25128.4 (2)C20—C21—C16123.0 (2) C21—N5—C25124.6 (2)N4—C22—N5112.5 (2) C2—C1—N1130.6 (2)N4—C22—C23123.8 (2) C2—C1—C6120.1 (2)N5—C22—C23123.7 (2) N1—C1—C6109.3 (2)C22—C23—C24111.8 (2) C3—C2—C1117.9 (2)C22—C23—H23A109.3C3—C2—H2A121.0C24—C23—H23A109.3C1—C2—H2A121.0C22—C23—H23B109.3C2—C3—C4121.4 (2)C24—C23—H23B109.3C2—C3—H3A119.3H23A—C23—H23B107.9C4—C3—H3A119.3C23—C24—H24A109.5C5—C4—C3121.6 (2)C23—C24—H24B109.5C5—C4—H4A119.2H24A—C24—H24B109.5C3—C4—H4A119.2C23—C24—H24C109.5C4—C5—C6116.6 (2)H24A—C24—H24C109.5C4—C5—H5A121.7H24B—C24—H24C109.5C6—C5—H5A121.7N5—C25—C26113.4 (2) N2—C6—C5132.0 (2)N5—C25—H25A108.9N2—C6—C1105.6 (2)C26—C25—H25A108.9C5—C6—C1122.4 (2)N5—C25—H25B108.9N1—C7—N2112.4 (2)C26—C25—H25B108.9N1—C7—C8122.6 (2)H25A—C25—H25B107.7N2—C7—C8124.9 (2)C27—C26—C30117.8 (2) C7—C8—C9110.5 (2)C27—C26—C25119.9 (2) C7—C8—H8A109.6C30—C26—C25122.3 (2) C9—C8—H8A109.6C28—C27—C26119.2 (3) C7—C8—H8B109.6C28—C27—H27A120.4C9—C8—H8B109.6C26—C27—H27A120.4H8A—C8—H8B108.1C29—C28—C27119.1 (3) C8—C9—H9A109.5C29—C28—H28A120.4C8—C9—H9B109.5C27—C28—H28A120.4H9A—C9—H9B109.5N7—C31—C32170.4 (9) C8—C9—H9C109.5C31—C32—H32A109.5H9A—C9—H9C109.5C31—C32—H32B109.5H9B—C9—H9C109.5H32A—C32—H32B109.5N2—C10—C11112.0 (2)C31—C32—H32C109.5N2—C10—H10A109.2H32A—C32—H32C109.5C11—C10—H10A109.2H32B—C32—H32C109.5。
掺杂氧化铁纳米晶对重金属离子的晶面依赖选择性吸附研究获进展
的调控 或限制作 用 。 基 于此研究 ， 未 来 有 望将 材料 的击 穿 场 强 提 高 １ ０ 倍 以
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器 件结构 。 该结构将Ｓ ＮＳ Ｐ Ｄ 器件 置于 微 纳光纤 的倏 逝场 内 ， 实现 纳米 线对
微 纳 光 纤 中传 输的光 子 吸收 。 光学 计 算 显示 ， 该 类 结构有 望 实现 高 吸收 效 率 的同时 ， 保 持很好地 宽谱特性 。 经过 上海微 系统所 巫博士君杰和 浙江大学 博 士徐 颖 鑫 等 近 ３ 年实 验 探 索 ， 科研 团 队研 制 出微 纳光 纤耦 合Ｓ ＮＳＰ Ｄ器
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得 超双 亲聚 氨酯海 绵材 料 。 该项 成果为 制备 具有特 殊 浸润性 能 的多孔 弹性材料
及 其复 合材料 提供 了新 思路 ， 在 催化 剂载体 和智 能高分 子复 合材料 领域 有望 获
得 应用 。
近 几年来 ， 金 属所 聚合物 复合 材料研 究 组致力 于纳 米纤 维素 与石 墨烯相 互
1,8-萘啶衍生物近年来在生物医药领域的应用探究
1,8-萘啶衍生物近年来在生物医药领域的应用探究罗建松;徐涛;张福叶;迟绍明【摘要】近年来1,8-萘啶衍生物在生物医疗领域的研究应用进展很快.随着大量新型1,8-萘啶化合物不断合成出来,并通过大量实验研究发现这类化合物具备良好的生物活性,与其相关的医药性质得到越来越多的开发与研究,在多种疾病治疗领域得到应用:可应用于抗菌,癌症治疗,消炎药等,同时1,8-萘啶类化合物还可用于治疗精神类疾病,如抗抑郁.1,8-萘啶化合物拥有广泛的生物医疗应用前景,随着更多新型1,8-萘啶衍生物不断合成,这类化合物的医药用途也将得到更加深入的研究和应用.【期刊名称】《云南民族大学学报（自然科学版）》【年(卷),期】2018(027)006【总页数】5页(P460-463,478)【关键词】1,8-萘啶化合物;生物医药;有机合成【作者】罗建松;徐涛;张福叶;迟绍明【作者单位】云南师范大学化学化工学院,云南昆明650500;云南师范大学化学化工学院,云南昆明650500;云南师范大学化学化工学院,云南昆明650500;云南师范大学化学化工学院,云南昆明650500【正文语种】中文【中图分类】O06-1萘啶化合物是一类重要的天然产物和药物结构单元，本身具有多种重要的生物学特性.其中1,8-萘啶衍生物以其与过渡金属配合物优良的光学结构性质及光稳定性，广泛用于特定金属离子和阴离子识别、荧光化学探针、化学传感器、发光材料、超分子、DNA及RNA识别与监测、细胞内特定离子及生物分子的识别、光物理研究领域、生物体免疫系统调节等等[1-7].近年来，随着新型1,8-萘啶衍生物的合成和深入研究，大大拓展了其应用范围，例如光化学治疗，生物活性材料，潜在的太阳能转换材料，人工光合作用等多领域的应用[8-10].同时1,8-萘啶衍生物具有广泛的生物医药用途，例如抗肿瘤、抗抑郁和抗焦虑、抗过敏、抗菌药、抗增殖、抗疟疾、可用作消炎药和止痛剂以及治疗高血压等等[11-15].随着不断对新衍生物的合成和探究，在治疗艾滋病(HIV)方面，1,8-萘啶衍生物也开始展现出优良的治疗能力.萘啶类化合物具有良好的开发应用前景，倍受相关科研工作者的关注.本文将介绍近几年来1,8-萘啶衍生物在生物医学方面的研究应用进展.1 近年来1,8-萘啶化合物的生物活性探究1.1 抗菌活性2016年，Chennam Kishan Prasad团队设计合成了3种新型1,8-萘啶的金属Cu、Co、Zn配合物[16]，并研究了这3种配合物的抗菌活性.该团队培养了4种细菌病原体(金黄色葡萄球菌，枯草芽孢杆菌，大肠杆菌和肺炎克雷伯菌)，在这4种菌株中分别加入相应的1,8-萘啶金属配合物，探究其对这4种细菌病原体的抑制作用，并将结果与相同浓度的标准抗菌药物氨苄青霉素进行比较，发现其中的1,8-萘啶金属Cu配合物(图1化合物1a)具有优秀的抗菌活性.SAKRAM B等采用无溶剂固相研磨反应的方法，合成了一系列新型1,8-萘啶化合物[17]，使用氨苄青霉素作为参考药物，在革兰氏阳性菌金黄色葡萄球菌和革兰氏阴性菌大肠杆菌菌株中对所有合成的产品进行了抗菌活性测试.并以灰黄霉素作为参考药物，在黑曲霉和假丝酵母菌株中测试化合物的抗真菌活性.其中2种化合物(图1化合物1b,1c)表现出很高的抗菌和抗真菌活性.1.2 癌症治疗Behalo Mohamed S等以2-氨基-6-(2-苯氧硫杂环己烷)-4-(2-噻吩)烟腈为起始原料合成的一系列1,8-萘啶衍生物[18]显示出了对乳腺癌和前列腺癌细胞良好的细胞毒性，尤其对前列腺癌细胞展现出非常显著的毒性作用.其中3种化合物(图2化合物2a，2b，2c)对前列腺癌细胞表现出最显著的细胞毒性作用，是潜在的前列腺癌治疗药物.据世卫组织统计，世界上所有死于癌症的人中，占比最大的为肺癌，平均每年约有156万人死于肺癌.化疗被认为是延缓肿瘤生长的主要治疗方法之一，然而化疗治疗癌症在杀伤肿瘤细胞的同时，也可能将正常细胞和免疫细胞一同杀灭，所以化疗是一种“两害相权取其轻”的治疗手段.因此，针对癌症的有效治疗药物有非常高的研发价值.THILAGAM S等合成了一系列基于1,8-萘啶化合物[19]，并测试了这系列化合物对人类癌症细胞的抑制作用.其中发现化合物2d(图2化合物2d)对A549系肺癌细胞具有很好的抑制活性.1.3 抗艾滋病病毒(HIV)活性探究早在2010年Massari Serena团队探究了在1,8-萘啶环C-7位碳原子上接入1-(1,3-苯并噻唑-2-)哌嗪基团(图3化合物3a)[20]，可在被感染的细胞中选择性识别和抑制HIV-1病毒的Tat介导转录蛋白酶，从而抑制HIV-1型病毒复制转录.众所周知，HIV-1是一种逆转录病毒，属于RNA病毒中的一种.逆转录病毒在其生命周期内需要完成将病毒遗传信息整合进宿主细胞核的行动.逆转录病毒自身的整合酶(Integrase)是帮助逆转录病毒把携带病毒遗传信息整合到宿主的DNA的酶.因此整合酶可以作为对抗HIV-1病毒的靶标.目前有3种经美国食品药品监督管理局(FDA)批准用于治疗艾滋病的HIV-1整合酶(IN)链转移抑制剂(INSTIs).基于此，Zhao[21]和Nagasawa[22]等设计合成了一系列新型1,8-萘啶化合物，并测定了这些化合物对HIV-1型病毒整合酶的抑制效果，发现化合物3b(结构见图3)的整体抑制效果最好.该团队还将继续设计合成出更多新型1,8-萘啶化合物并探究对HIV-1型病毒整合酶的抑制效果.1.4 抗抑郁治疗抑郁症是全球一种常见病，据世界卫生组织(WHO)估计共有3.5亿名患者.长期的中度或重度抑郁症可能成为一个严重的疾患.最严重时，抑郁症可引致自杀.每年自杀死亡人数估计高达100万人.WHO预测，到2020年，抑郁症将是全球过早死亡或残疾的第二大原因.根据《精神疾病诊断与统计手册》(DSM-IV)特征，抑郁症的症状表现在正常日常活动和悲伤感中丧失兴趣或乐趣.其他的症状包括内疚感或自卑感，睡眠不足或食欲不振，无精打采.甚至，抑郁症可导致自杀.抑郁症患者自杀率高达3.4%.虽然有许多临床上有用的抗抑郁药物可用，但疾病的流行仍然存在.这可能是由于目前可用的药物功效不足，缺乏对抑郁症病因和病理机制的清晰认识.DharArghya K团队分别在2014年和2015年设计合成了一系列1,8-萘啶衍生物[23-24]，并测试了这些化合物的抗抑郁效果.其中的3种化合物(图4化合物4a，4b，4c)在小鼠实验中取得了不错的抗抑郁效果.该团队将在相关课题中进行更深入的研究.1.5 消炎药DI BRACCIO M等设计合成的一系列新型1,8-萘啶化合物[25]，并测定发现这些化合物均具备良好的抗炎活性，其中化合物5a(结构见图5)在大鼠体内表现出良好的抗炎性质，是潜在的抗炎药物.该团队在小鼠止痛测试中还发现，化合物5a还表现出良好的止痛作用，是有效的消炎和止痛效果的药物.2 小结1,8-萘啶类化合物拥有广泛的生物活性，目前已经在多种疾病治疗中表现出了较为出色的治疗效果.随着新型的1,8-萘啶衍生物不断合成出来，这类化合物的生物医药活性具有巨大潜在的探究价值.同时伴随有机合成技术的发展，必将出现更有针对性、治疗效果更佳、副作用更低的1,8-萘啶有机化合物，作为有机合成的热点并将在生物医药领域继续得到广泛研究.参考文献:【相关文献】[1] HUANG M, LOU Z, PENG X, et al. 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Bis(acetato-j 2O ,O H )(2,9-dimethyl-1,10-phenanthroline-j 2N ,N H )-mercury(II)in two differently hydrated crystal formsMiguel Angel Harvey,a,b Sergio Baggio,b,c Andre Âs Iban Äez dand Ricardo Baggio e *aUniversidad Nacional de la Patagonia,Sede Trelew,9100Trelew,Chubut,Argentina,b CenPat,CONICET,9120Puerto Madryn,Chubut,Argentina,cUniversidad Nacional de la Patagonia,Sede Puerto Madryn,9120Puerto Madryn,Chubut,Argentina,d Departamento de FõÂsica,Facultad de Ciencias Fisicas y MatemaÂticas,Universidad de Chile,Casilla 487-3,Santiago de Chile,Chile,and eDepartmento de Fisica,ComisioÂn Nacional de Energia Atomica,Buenos Aires,ArgentinaCorrespondence e-mail:baggio@.ar Received 13May 2004Accepted 10June 2004Online 21July 2004Two differently hydrated crystal forms of the title compound,viz .bis(acetato- 2O ,O H )(2,9-dimethyl-1,10-phenanthroline- 2N ,N H )mercury(II),[Hg(C 2H 3O 2)2(C 14H 12N 2)]or [HgAc 2-(dmph)][dmph is 2,3-dimethyl-1,10-phenantroline (neo-cuproine)and Ac is acetate],(I),and tris[bis(acetato- 2O ,O H )-(2,9-dimethyl-1,10-phenanthroline- 2N ,N H )mercury(II)]hexa-decahydrate,[Hg(C 2H 3O 2)2(C 14H 12N 2)]3Á16H 2O or [HgAc 2-(dmph)]3Á16H 2O,(II),are presented.Both structures are composed of very simple monomeric units,which act as the building blocks of complex packing schemes stabilized by a diversity of %±%and hydrogen-bonding interactions.CommentThe weak interactions responsible for the self-assembly of metal±organic systems have become the main topic of many structural reports,with the result that the molecular building blocks themselves end up being viewed as merely supporting media for these interactions to occur.The presence ofwatermolecules and/or polycyclic aromatic ligands often sets favourable conditions for the appearance of these interactions.In these cases,the resulting complexes are usually prone to generating a variety of strong packing interactions,such as hydrogen bonds or medium-range contacts linking aromaticrings,either in a slipped or displaced stacking arrangement (hereinafter %±%)or in an edge(or point)-to-face conforma-tion (CÐH ÁÁÁ%)[for details,see Janiak (2000)].We present here the two title mercury acetate complexes,[HgAc 2(dmph)][dmph is dimethyl-1,10-phenantroline (neo-cuproine)and Ac is acetate],(I),and [HgAc 2(dmph)]3Á-16H 2O,(II),which may well constitute such cases.By means of a simple and rather predictable monomeric unit,[HgAc 2(dmph)],which both structures share as their elemental building block,two very different three-dimen-sional structures are built up,with an unusual number and diversity of packing interactions which are interesting from a structural point of view.Acta Crystallographica Section CCrystal Structure CommunicationsISSN0108-2701Figure 2Molecular diagram for (II).Displacement ellipsoids are drawn at the 40%probability level and H atoms have been omitted.For clarity,sequential atom labels C2A ±C9A ,C2B ±C9B and C2C ±C9C have beenomitted.Figure 1Molecular diagram for (I).Displacement ellipsoids are drawn at the 40%probability level.H atoms are not shown.The monomeric building units in (I)and (II)are composed of an Hg 2+cation coordinated by three chelating ligands (one dmph and two acetate anions),providing an uneven six-coordinated environment for the cation.Due to the narrow bite of the ligands,the coordination polyhedra deviate from any regular geometry and the most adequate description is that of a square pyramid,in which atoms N1,N2,O1A and O1B de®ne the base and the pair of atoms O1B and O2B occupy the apex.(In fact,the apical direction is represented by the C1B ÁÁÁHg line.)In order to quantify these assertions,we quote here some values for structure (I),but these are representative of all four independent units:the mean devia-tion of atoms N1,N2,O1A and O1B from the best plane is0.039(1)AÊ,with the cation displaced 1.05(1)A Êfrom the plane towards the apex,and the deviation of the C1B ÁÁÁHg line from the base normal is 7.9(1) .While this molecular unit is the only motif present in (I),the asymmetric unit of (II)is composed of three independent such [HgAc 2(dmph)]groups complemented by 16hydration water molecules,for which the description of the intermolecular interactions becomes much more complex.Inspection of Figs.1and 2,which present the four inde-pendent [HgAc 2(dmph)]units in both structures,con®rmsFigure 3A schematic diagram showing the %±%interactions between dmph groups in (I).Primed labels denote atoms at the symmetry position (Àx ,1Ày ,1Àz).Figure 4Schematic diagrams showing the %±%interactions between dmph groups in (II).(a )The A H ±A interaction,with primed labels denoting atoms at the symmetry position (2Àx ,1Ày ,2Àz );(b )the A ±B interaction;(c )the B ±C interaction;(d )the C ±C HH interaction,with doubly primed labels denoting atoms at the symmetry position (2Àx ,1Ày ,1Àz ).their topological similarity.There remain,however,some geometric differences which might well have to do with packing processes(see below)and which can be analysed from the values in Tables1and3,where surveys of relevant bond distances and angles around the cations are presented.In order to facilitate the comparison of homologous parameters, they have been grouped so that they appear in the list in the same sequence.The dmph ligand binds,as usual,in a very symmetric fashion.The maximum difference in bond lengths corresponds to structure(II),where the difference in HgÐN distances is approximately twice the sum of the individual s.u.values,the remainder not being signi®cant.In all four cases,the coordi-nation plane through the cation is almost coincident with the ligand plane,with a maximum deviation of2.1(1) displayed in structure(I).All four cations[one in(I)and three in(II)]are coordi-nated by two acetate groups behaving quite differently.One of them binds symmetrically[unit A in(I),and units D,G and I in (II)],the other[unit B in(I),and units E,F and H in(II)] being asymmetric and presenting,in all cases but unit H,both the shortest as well as the longest coordination distances, with some of these last even being beyond normally accep-ted coordination distances[viz.Hg2ÐO2F=2.752(5)AÊ, compared with the SHELXL97(Sheldrick,1997)default value of2.66AÊ].The extreme availability in both structures of pyridyl and aryl cycles prone to forming%±%contacts,and the large number of water molecules able to participate in hydrogen-bonding[in structure(II)]lead to very rich interaction schemes for these two compounds.In structure(I),the main interaction present is the%±% bond shown in Fig.3,which links the monomeric [Hg(dmph)Ac2]building-block units into`dimers',which are in fact the real structural motifs(Table2).These units are in turn isolated in space,their interaction being much weaker and achieved through diffuse van der Waals forces. Structure(II)can be described as chains of%±%-bonded monomers piled up on top of one another and aligned along the c axis,interlinked by a dense network of hydrogen-bonded water molecules.Monomers stack in the column in the sequence CBA.ABC.CBA,where the dot(.)denotes a symmetry centre and A,B and C represent the suf®xes char-acterizing the aromatic ligands in each monomer.Thus,there are four different types of%±%contacts,which can be repre-sented(using the above coding)as A.A,AB,BC and C.C. These are sketched in Fig.4and the relevant parameters are given in Table4.The columns thus formed are connected to each other via a hydrogen-bond network,which could be deduced from the O-atom positions as it was not possible to locate water H atoms with any degree of con®dence in the presence of Hg.In spite of this limitation,the linkages are very clear,as shown in Fig.5.All water H atoms take part in this hydrogen-bond network,with OÁÁÁO separations in the range2.439(17)±2.985(17)AÊ.ExperimentalCompound(I)was prepared by direct mixing of a methanolic solu-tion of Hg acetate and neocuproine with an aqueous solution of potassium persulfate,in such a way as to have0.025M®nal concentrations for all reagents.The solid material obtained after a few days was recrystallized from dimethylformamide,yielding pale-yellow pound(II)was prepared by diffusion of an aqueous solution of potassium sulfate into a methanolic solution of Hg acetate and neocuproine through a very thin capillary initially full of water(all reagents in0.025M concentration).After a couple of days,pale-yellow prisms suitable for X-ray diffraction were obtained. The overwhelming number of crystallization water molecules in(II) renders the structure quite unstable at room temperature,to the extent that a single crystal usually survives just a few seconds under ambient conditions before collapsing.Sealed in a capillary with a drop of mother liquor,however,they can remain unaltered for weeks.Compound(I)Crystal data[Hg(C2H3O2)2(C14H12N2)]M r=526.93Triclinic,P1a=8.3619(15)AÊb=9.4973(18)AÊc=12.349(2)AÊ=83.167(3)=76.646(4)=66.027(3)V=871.5(3)AÊ3Z=2D x=2.008Mg mÀ3Mo K radiationCell parameters from187re¯ections=2.0±25.0"=8.86mmÀ1T=293(2)KPrism,pale yellow0.25Â0.14Â0.10mmData collectionBruker SMART CCD area-detectordiffractometer9and3scansAbsorption correction:multi-scan[SADABS(Sheldrick,1996)inSAINT(Bruker,2000)]T min=0.22,T max=0.417356measured re¯ections3659independent re¯ections1839re¯ections with I>2'(I)R int=0.054max=28.0h=À10311k=À11311l=À11315Figure5A packing view of(II)down the(110)direction,showing two columns connected by a dense network of crystallization water molecules.The columns one level above and below the water network(which complete a four-column environment of the water network)have been omitted for clarity.Re®nementRe®nement on F2R [F 2>2'(F 2)]=0.050wR (F 2)=0.084S =0.813659re¯ections 230parametersH-atom parameters constrained w =1/['2(F o 2)+(0.0119P )2]where P =(F o 2+2F c 2)/3(Á/')max =0.007Á&max =0.76e A ÊÀ3Á&min =À0.78e AÊÀ3Compound (II)Crystal data[Hg(C 2H 3O 2)2(C 14H 12N 2)]3Á16H 2O M r =1869.03Triclinic,P 1a =13.738(3)A Êb =14.076(3)A Êc =20.615(4)A Ê =93.11(3)=90.85(3) =118.93(3)V =3480.2(16)AÊ3Z =2D x =1.784Mg m À3Mo K radiationCell parameters from 277re¯ections =2.3±23.8 "=6.68mm À1T =293(2)K Prism,pale yellow 0.18Â0.16Â0.12mm Data collectionBruker SMART CCD area-detector diffractometer 9and 3scansAbsorption correction:multi-scan [SADABS (Sheldrick,1996)in SAINT (Bruker,2000)T min =0.31,T max =0.4529254measured re¯ections14989independent re¯ections 9362re¯ections with I >2'(I )R int =0.034 max =28.0 h =À17317k =À18317l =À26326Re®nementRe®nement on F 2R [F 2>2'(F 2)]=0.045wR (F 2)=0.114S =1.0114989re¯ections 820parametersH-atom parameters constrained w =1/['2(F o 2)+(0.0484P )2]where P =(F o 2+2F c 2)/3(Á/')max =0.010Á&max =0.77e A ÊÀ3Á&min =À0.77e AÊÀ3Aromatic H atoms were placed at calculated positions (CÐH =0.93AÊ)and allowed to ride on their parent atoms,while those of the terminal methyl groups were not included in the models because they could not be con®dently positioned.A similar situation arose with the H atoms of the water molecules,which could not be reliably located in the presence of Hg,so they were disregarded from the model and the hydrogen-bonding interactions were discussed solely in terms of O ÁÁÁO distances.Full use of the CCDC package was made for searching the Cambridge Structural Database (Allen,2002).For both compounds,data collection:SMART (Bruker,2001);cell re®nement:SMART ;data reduction:SAINT (Bruker,2000);program(s)used to solve structure:SHELXS 97(Sheldrick,1997);program(s)used to re®ne structure:SHELXL 97(Sheldrick,1997);molecular graphics:XP in SHELXTLPC (Sheldrick,1994);software used to prepare material for publication:SHELXL 97.The authors acknowledge the Spanish Research Council (CSIC)for provision of a free-of-charge licence to the CSD.Supplementary data for this paper are available from the IUCr electronic archives (Reference:HJ1012).Services for accessing these data are described at the back of the journal.ReferencesAllen,F.H.(2002).Acta Cryst.B 58,380±388.Bruker (2000).SAINT .Version 6.02a.Bruker AXS Inc.,Madison,Wisconsin,USA.Bruker (2001).SMART .Version 5.624.Bruker AXS Inc.,Madison,Wisconsin,USA.Janiak,C.(2000).J.Chem.Soc.Dalton Trans.pp.3885±3898.Sheldrick,G.M.(1996).SADABS .University of GoÈttingen,Germany.Sheldrick,G.M.(1994).SHELXTL /PC .Version 5.0.Siemens Analytical X-ray Instruments Inc.,Madison,Wisconsin,USA.Sheldrick,G.M.(1997).SHELXS 97and SHELXL 97.University ofGoÈttingen,Germany.Table 3Selected geometric parameters (AÊ, )for (II).Hg1ÐO2E2.256(6)Hg1ÐN2A 2.306(5)Hg1ÐN1A 2.313(5)Hg1ÐO1D 2.384(5)Hg1ÐO2D 2.529(6)Hg1ÐO1E 2.547(6)Hg2ÐO1F 2.197(5)Hg2ÐN1B 2.282(6)Hg2ÐO2G 2.291(6)Hg2ÐN2B 2.309(5)Hg2ÐO1G 2.626(6)Hg2ÐO2F 2.752(5)Hg3ÐO1I 2.285(6)Hg3ÐN2C 2.305(6)Hg3ÐN1C 2.307(5)Hg3ÐO2H 2.310(5)Hg3ÐO2I 2.518(6)Hg3ÐO1H 2.637(7)N1A ÐHg1ÐN2A 72.51(19)O1D ÐHg1ÐO2D 52.0(2)O1E ÐHg1ÐO2E 51.8(2)N1B ÐHg2ÐN2B 73.2(2)O1G ÐHg2ÐO2G50.0(2)O1F ÐHg2ÐO2F 50.45(18)N1C ÐHg3ÐN2C 73.0(2)O1I ÐHg3ÐO2I 52.6(2)O1H ÐHg3ÐO2H50.7(2)Table 2%±%contacts for (I).Group 1/Group 2IPD (A Ê)CCD (A Ê)SA ( )C4±C7,C11,C12/N1H ,C1H ±C4H ,C12H3.46(1)3.62(1)18.2(2)Notes:see Fig.3for details of the atom labelling and symmetry code;IPD is theinterplanar distance,CCD is the centre-to-centre distance and SA is the slippage angle.Table 1Selected geometric parameters (AÊ, )for (I).HgÐO1B2.188(6)HgÐN1 2.303(7)HgÐN2 2.310(7)HgÐO1A 2.380(6)HgÐO2A 2.486(7)HgÐO2B 2.723(8)N1ÐHgÐN272.1(3)O1A ÐHgÐO2A52.9(2)O1B ÐHgÐO2B50.3(2)Table 4%±%contacts for (II).Group 1/Group 2IPD (A Ê)CCD (A Ê)SA ( )N2A H ,C7A H ±C11A H /N1A ,C1A ±C4A ,C12A3.40(1) 3.60(1)19.2(2)C4A H ±C7A H ,C11A H ,C12A H /C4A ±C7A ,C11A ,C12A3.39(1) 3.67(1)22.4(2)N2A ,C7A ±C11A /N1B ,C1B ±C4B ,C12B3.45(1) 3.51(1)21.0(2)C4A ±C7A ,C11A ,C12A /C4B ±C7B ,C11B ,C12B3.45(1) 3.55(1)13.7(2)N2B ,C7B ±C11B /N1C ,C1C ±C4C ,C12C3.45(1) 3.54(1)13.1(2)C4B ±C7B ,C11B ,C12B /C4C ±C7C ,C11C ,C12C3.43(1) 3.51(1)10.7(2)N2C ,C7C ±C11C /N1C HH ,C1C HH ±C4C HH ,C12C HH3.42(1) 3.64(1)20.2(2)C4C ±C7C ,C11C ,C12C /C4C HH ±C7C HH ,C11C HH ,C12C HH3.43(1)3.68(1)22.4(2)Notes:see Fig.4for details of the atom labelling and symmetry codes;IPD is theinterplanar distance,CCD is the centre-to-centre distance and SA is the slippage angle.。