对称四甲基六元瓜环与Ca(Ⅱ)生成的自组装超分子配合物的晶体结构

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对称四甲基六元瓜环与4-二甲胺基吡啶衍生物的自组装模式

对称四甲基六元瓜环与4-二甲胺基吡啶衍生物的自组装模式涂仕春;杨波;肖昕;薛赛凤;陶朱【摘要】利用1H NMR、质谱和紫外吸收光谱法考察了主体对称四甲基六元瓜环(TMeQ[6])与客体4-二甲胺基吡啶(DP)、N-丁基-4-二甲胺基吡啶碘化物(C4DP+)的自组装模式.结果表明,TMeQ[6]包结DP的吡啶环部分,而与C4DP+自组装时,则优先包结烷基链部分形成1∶1的类轮烷结构.【期刊名称】《贵州大学学报（自然科学版）》【年(卷),期】2014(031)002【总页数】4页(P13-16)【关键词】瓜环;类轮烷;超分子【作者】涂仕春;杨波;肖昕;薛赛凤;陶朱【作者单位】贵州省大环化学及超分子化学重点实验室,贵州贵阳550025;贵州省大环化学及超分子化学重点实验室,贵州贵阳550025;贵州省大环化学及超分子化学重点实验室,贵州贵阳550025;贵州省大环化学及超分子化学重点实验室,贵州贵阳550025;贵州省大环化学及超分子化学重点实验室,贵州贵阳550025【正文语种】中文【中图分类】O625自从2000年六元瓜环(Q［6］)的同系物五、七、八以及十元瓜环(Q［5］、Q ［7］、Q［8］、Q［10］)面世以来，建立在瓜环分子识别功能以及自组装超分子构件特质基础上的瓜环化学研究受到国内外越来越多的研究者的关注［1］，但由于瓜环仅微溶于水，使其应用研究受到明显的制约。

因此改性瓜环的合成近年来也成为了瓜环研究的一个重要课题。

1992年，Stoddart等首先合成得到了聚合度为5的十甲基五元瓜环［2］。

随后，一系列的改性瓜环被合成并分离，如间位取代六甲基六元瓜环、十二甲基六元瓜环、对称四甲基六元瓜环［3－6］、羟基取代五元及六元瓜环［7］、二苯基取代六元瓜环［8］、环戊基取代瓜环［9－11］等。

近期，瓜环家族中最大成员—铰接十四元瓜环被本课题组首次发现并报道，单晶X－射线结果表明十四元瓜环是由14个苷脲单体通过28个亚甲基桥联形成折叠“8”字形的笼状化合物，铰接十四元瓜环(tQ［14］)具有很好的水溶性，并能溶于二甲亚砜、二甲基甲酰胺等极性有机溶剂，且具有良好的骨架伸缩柔韧性［12］。

笼状化合物--瓜环与六次甲基四胺自组装结构的NMR研究

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第 48 卷第 22 期 2003 年 11 月
简报
图 6 HMTA 和 Q[7]的 1H NMR 谱图
(a) HMTA︰Q[7]~1.5︰1, (b) HMTA︰Q[7] ~ 9︰1
图 7 HMTA HCl 和 Q[7]的 1H NMR 谱图
(a) HMTA︰Q[7] ~ 1︰1, (b) HMTA︰Q[7] ~ 3.5︰1

简报
第 48 卷第 22 期 2003 年 11 月
图 3 HMTA-Q[5]-HMTA-Q[5]-HMTA 自组装分子胶囊壳(a)或超分子 Q[5]是以何种健合方式发生作用, 我们推测可能是 HMTA 的氮通过水分子作为氢键键桥与瓜环端口的氧形成 =N··H-O-H···O C=的形式进行结合.
简报
图 2 HMTA-Q[5]的 1H NMR 谱图
(a) HMTA ︰Q[5] ~1︰1, (b) HMTA ︰Q[5]~5︰1, (c) HMTA︰Q[5]~10︰1
图 1 HMTA 在氘代水中的 NMR 谱图
图 2 所示为不同摩尔比的 HMTA 与 Q[5]的 1H NMR 谱. 图中对各种质子峰进行了归属, 其中带“ ” 的为在瓜环端口具有相互作用的峰.
2.2 HMTA 与 Q[5]的作用 HMTA 是一种对称性很高的笼状结构分子 , 所以
在它的 1H NMR 谱图中, 只有一个单峰(如图 1 所示). 当 HMTA 与瓜环在端口或笼体相互作用形成自组装 (超分子)或包结配合物时, 由于瓜环的屏蔽或去屏蔽作用, 导致其亚甲基上质子的化学环境发生变化, 从而使 HMTA 质子的化学位移有所不同 . 根据核磁共振谱提供的信息, 可较准确地了解因相互作用形成自组装(超分子)或包结配合物的结构特征, 推测其基本性质 .

钾离子为底的对称四甲基六元瓜环分子碗

２０１４年８月
兴义民族师范学院学报
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Ａｕｇ．２０１４Ｎｏ．４
第４期
钾离子为底的对称四甲基六元瓜环分子碗
易君明１，２陈明华吕春张云黔薛赛凤
（１．兴义民族师范学院，贵州兴义５６２４００；２．贵州大学，贵州贵阳５５００２５）
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Ａｂｓｔｒａｃｔ：ＡｎｏｖｅｌｍｏｌｅｃｕｌａｒｂｏｗｌｂａｓｅｄｏｎＴｅ￣ａｍｅｈｔｙｌＳｕｂｓｔｉｔｕｔｅｄＣｕｃｕｒｂｉｔ［６］ｕｒｉｌ（ＴＭｅＱ［６］）ａｎｄｐａｔａｓｓｉｕｍｃａｔｉｏｎｗｅｒｅｓｙｎｔｈｅ－

对称四甲基取代六元瓜环对醋酸地塞米松的增溶作用

时，利用共溶剂法制备了ＴＱ６与醋酸地塞米松的固体包结物，还Ｍｅ［］并对其主客体作用进行了ＤＡ研究。Ｔ
关键词对称四甲基取代六元瓜环，醋酸地塞米松，增溶，包结物文献标识码：Ａ文章编号：０００１（０００－５３０１０－５８２１）５０６－４中图分类号：６５１０４．
衍生物ＴＱ［］如Ｓｈｍｂ作为主体，Ｍｅ６（ｃｅｅｌ）通过微孔滤膜分离和ＤＡ的方法研究了它对醋酸地塞米松Ｔ的增溶作用、成包结物的条件及包结物性质。目前，增溶方面的研究主要采用紫外分光光度形在法，方法忽略了主客体包结后会造成吸光度值变化的影响，外，低浓度下测得的回归曲线容该另极
２０￣７００９－９收稿，０９１—７修回２０ —０１
教育厅科技（Ａ８５）校教师科研启动经费资助项目Ｊ０１７、
通讯联系人：李国平，，师；Ｅｍｉｌｕｐｎ－０＠１３ｃｆ；男讲 — ａｌｉｏｉｇ０３６．ｏａ研究方向：：ｇ２大环与超分子化学
第２７卷第５期２１００年５月
应用化学
ＣＨＩＳＯＵＲＮＰＩＨＥＭＩＴＲＮＥＥＪＡＬＯＦＡＰＬＥＤＣＳＹ
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对称四甲基取代六元瓜环对醋酸地塞米松的增溶作用

三种六元瓜环与 Sr髤离子的配位及超分子自组装

Ａｂｓｔｒａｃｔ：Ｉｎｔｈｅｐｒｅｓｅｎｔｗｏｒｋ，ｔｈｒｅｅｄｉｆｆｅｒｅｎｔｃｕｃｕｒｂｉｔ［６］ｕｒｉｌｓ（Ｑ［６］ｓ），ｔｈｅｕｎｓｕｂｓｔｉｔｕｔｅｄｃｕｃｕｒｂｉｔ［６］ｕｒｉｌ，１，３，５一
子时，Ｑ［６］ｓ — Ｓ Ⅱ ）离子形成配位聚合链，而只有ＮＯｒ离子存在时，形成水分子配位桥连的超分子链。
关键词：六元瓜环；甲基取代六元瓜环（Ｑ［６】ｓ）；ｓ１（１Ｉ）离子；超分子自组装；晶体结构
国家自然科学基金项目（Ｎｏ．２１２７２０４５）、教育部“ 春晖计划 ” （Ｎｏ．Ｚ２００８ — １．５５００１）、贵州省科学技术基金（Ｎ０．Ｊ２００９．２０２４）资助项目。
通讯联系人。Ｅ－ｍａｉｌ：ｓｃｉ．ｙｑｚｈａｎｇ＠ｇｚｕ．ｅｄｕ．ｏｎ
在Ｑ［６１与ＳｒＣ１，的盐酸溶液中引入１，４．二氧六
环．很容易得到包结了二氧六环的Ｑ［６１一Ｓｒ（Ｈ）离子配
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第３０卷
Ｓａｉ — Ｆｅｎｇ（薛赛凤），ｅｔａ１．Ｓｃｉ．ＣｈｉｎａＳｅｔ．Ｂ（中国科学Ｂ辑），

钾离子为底的对称四甲基六元瓜环分子碗

钾离子为底的对称四甲基六元瓜环分子碗易君明;陈明华;吕春;张云黔;薛赛凤【摘要】对称四甲基六元瓜环(TMeQ [6])与钾离子(K+)在稀盐酸水溶液中相互作用形成配合物,用单晶-X射线衍射仪测试其晶体结构.测试结果表明,配合物形成以TMeQ[6]为“碗体”,钾离子为“碗底”的“分子碗”结构,相邻配合物结构单元之间通过氢键或配位键连接形成一维超分子链.【期刊名称】《兴义民族师范学院学报》【年(卷),期】2014(000)004【总页数】5页(P108-112)【关键词】对称四甲基六元瓜环;钾离子;配合物;晶体结构;分子碗【作者】易君明;陈明华;吕春;张云黔;薛赛凤【作者单位】兴义民族师范学院,贵州兴义 562400;贵州大学,贵州贵阳 550025;兴义民族师范学院,贵州兴义 562400;兴义民族师范学院,贵州兴义 562400;贵州大学,贵州贵阳 550025;贵州大学,贵州贵阳 550025【正文语种】中文【中图分类】O614分子容器是超分子化学研究的重要内容之一，通常是由一端或两端开口且具有空腔结构的大环刚性有机分子和有机或无机小分子构成,分子之间的高效选择性识别是合成分子容器的关键步骤，这种选择识别可以通过尺寸匹配、离子-偶极、疏水作用、氢键等多种因素进行调控[1-2]。

瓜环(cucurbit[n]urils,缩写为Q[n],n=5,6,7,8,10)[3,4]是继冠醚、环糊精、杯芳烃之后发展起来新型大环超分子主体化合物，具有疏水性空腔和极性羰基氧原子围绕的两端口，不同聚合度的瓜环可以选择性地与金属离子进行配位构成结构新颖的自组装实体或超分子结构[5,6]，具有广阔的应用前景和开发潜力。

但是普通瓜环除七元瓜环外水溶性均不太好，水溶性较好的对称四甲基六元瓜环(TMeQ[6])[7]的面世,不仅增加了新的瓜环家族成员，而且使瓜环化学在水中的研究成为可能，拓宽了瓜环化学的应用研究领域，因其具有与普通六元瓜环相似的几何结构尺寸，而且具有较好的水溶性，受到瓜环化学工作者的重视[8-11]。

在四氯合锌离子诱导下反式六元瓜环与碱金属离子构筑的配位超分子自组装体

在四氯合锌离子诱导下反式六元瓜环与碱金属离子构筑的配位超分子自组装体邱胜超;李青;张云黔;肖昕;陶朱;祝黔江;张振琴【摘要】在盐酸介质中,通过四氯合锌离子诱导,碱金属离子能与反式六元瓜环端口羰基氧原子直接配位构筑形成超分子自组装体.单晶结构表明在HCl介质中,四氯合锌离子形成“蜂巢结构”,而且在[ZnCl4]2-诱导作用下,碱金属离子和反式六元瓜环端口羰基氧直接配位形成一维超分子自组装体而填充在“蜂巢结构”中.【期刊名称】《无机化学学报》【年(卷),期】2016(032)007【总页数】8页(P1303-1310)【关键词】碱金属离子;反式六元瓜环;四氯合锌根离子;超分子自组装体【作者】邱胜超;李青;张云黔;肖昕;陶朱;祝黔江;张振琴【作者单位】贵州大学化学与化工学院,贵州省大环化学及超分子化学重点实验室,贵阳 550025;贵州大学化学与化工学院,贵州省大环化学及超分子化学重点实验室,贵阳 550025;贵州大学化学与化工学院,贵州省大环化学及超分子化学重点实验室,贵阳 550025;贵州大学化学与化工学院,贵州省大环化学及超分子化学重点实验室,贵阳 550025;贵州大学化学与化工学院,贵州省大环化学及超分子化学重点实验室,贵阳 550025;贵州大学化学与化工学院,贵州省大环化学及超分子化学重点实验室,贵阳 550025;南京医科大学药学院化学系,南京210009【正文语种】中文【中图分类】O614.24+1;O614.112;O614.113;O614.114An inverted cucurbit[6]uril(i Q[6],Fig.1)was first reported by Isaacs and Kim in 2005[1-2],and since then only a couple of theoretical investigations on their potential properties have been reported[3-4].A low synthetic yield and difficulties in separating i Q[n]s has hindered their investigation.Upon their discovery,it was suggested that i Q[n]s could selectively recognize guests by the shape and dimensions of their cavity[4].Indeed,X-ray crystallographyand1HNMR spectroscopy revealed interesting host-guest interactions between i Q[6]and p-phenylenediaminium in both the solid state and aqueous solution.Two different complexes were observed in the solid state:an inclusion structure and a sandwich structure.In aqueous solution,the i Q [6]host can accommodate the p-phenylenediaminium guest,but the guest favours staying outside the pores of the i Q[6]host,and guest exchange is fast on the NMR time scale[5].We recently developed a convenientmethod for isolating i Q[6]from the normal cucurbit[6]uril(Q[6]) by column chromatography using a Dowex resin[6]. Then we investigated the coordination properties of i Q[6]with variousmetal ions.Obtaining solid crystals of i Q[6]/M+by simplymixing i Q[6]with alkali salts was proved difficult,without the addition of a structure directing agent such as tetrachloride zincate anion ([ZnCl4]2-).However,in thepresenceof[ZnCl4]2-,reaction of alkaline earth cations(AE2+)and the inverted cucurbit[6]uril(i Q[6])yielded linear coordination polymers in which i Q[6]and AE2+cations are directly coordinated to themetal ions.In contrast,in the i Q[6]-Mg2+-[ZnCl4]2-HCl system,there was no directcoordination between i Q[6]and Mg2+or Zn2+,presumably due to the shorter ionic radii preventing direct coordination[6].Recently,we found that the coordination of i Q[6]with Ln3+gave rise to differentinteraction products and isomorphous groups with the heavier lanthanides. The interaction of i Q[6]with lighter lanthanides such as La3+,Ce3+,Pr3+and Nd3+immediately yielded precipitation or single crystal solids,whereas interaction of i Q[6]with Sm3+and Eu3+did notgenerate solidmaterial. Interaction of i Q[6]with heavier lanthanides gave rise to three isomorphous groups with different structure features,withGd3+,Tb3+,Dy3+and Ho3+forming one group,Er3+,Tm3+andYb3+forming a separate group, and Lu3+differing from both of these groups[7].In the present work,i Q[6]was used as a ligand, and its coordination with alkali cations(M+)in supramolecular assemblieswas investigated in the presence of the structure directing agent[ZnCl4]2-.Single-crystal X-ray diffraction analysis revealed that the i Q[6]-M+-[ZnCl4]2--HCl interaction systems consisted of a supramolecular assembly of iQ[6]/M+complexesand[ZnCl4]2-anions,in which[ZnCl4]2-anions are assembled into a honeycomb-like frameworks via outer surface interactions between i Q[6]s.The linear coordination polymers of iQ[6]hosts coordinated to M+cations(A=Na,K,Rb) fill the poresorchannels in the[ZnCl4]2-framework[8-10].1.1 Reagents and instrumentAll chemicals including alkali metal chlorides (MCl)were of reagent gradeand were used without further purification.i Q[6]was prepared as described previously[1].Elemental analysiswas carried out on a EURO EA-3000 elemental analyzer.1.2 Preparation of titled com poundsA similar process was used to prepare crystals forall i Q[6]-M+-[ZnCl4]2--HCl systems.Specifically,MCl (0.15 mmol,M=Na,K,Rb)andZnCl2(14.79mg,0.12 mmol)were dissolved in 1 mLH2O to prepare solution A,and i Q[6](20 mg,0.015 mmol)was dissolved in 1 mL 6 mol·L-1HCl to prepare solution B.Solution B was then slow ly added to solution A and stirred.X-ray diffraction-quality crystals were obtained by slowly evaporation after 7 days.[Na2(H2O)2(i Q[6])]·[ZnCl4]·[Zn(H2O)Cl3](H3O)· 7H2O(1):Anal.Calcd.forC36H59N24O23Na2Zn2Cl7(%):C,26.68,H,3.67,N,20.74;Found(%):C,26.87,H,3.56, N,21.01.{K4(H2O)8[ZnCl4](i Q[6])2}·[ZnCl4]·3[Zn(H2O)Cl3](H3O)3·22H2O(2):Anal.Calcd.forC72H147N48O60K4Zn5Cl17(%):C,23.18,H,3 .97,N,18.02;Found(%):C,23.28, H,3.76,N,18.21.[Rb(H2O)(i Q[6])]·[ZnCl4]·[Zn(H2O)Cl3](H3O)2· 16H2O(3):Anal.Calcd.forC36H78N24O32RbZn2Cl7(%): C,23.71,H,4.31,N,18.43;Found(%):C,23.84,H, 4.13,N,18.77.1.3 X-ray crystallographyA suitable single crystal(～0.2 mm×0.2 mm×0.1 mm)was embedded in paraffin oil and mounted on a Bruker SMART ApexⅡCCD diffractometer equipped with a graphite-monochromated Mo Kαradiation source(λ=0.071 07 3 nm,μ=0.828mm-1),which was operated in theω-scan mode under a nitrogen stream(-50℃). Datawere corrected for Lorentz and polarization effects using the SAINT program[11],and semi-empirical absorption corrections based on equivalent reflections were applied using the SADABS program[12].The structure was elucidated through directmethods,and full-matrix least-squares refinement of F2values was performed using SHELXS-97[13]and SHELXL-97[14].All nonhydrogen atomswere refined anisotropically,and carbon -bound hydrogen atoms were introduced at calculated positions and treated as riding atoms with an isotropic displacement parameter equal to 1.2 times that of the parent atom.Most of the watermolecules were omitted using the SQUEEZE option of the PLATON program[15]. A total of 8,including 1 protonated watermolecules, 25,including 3 protonated water molecules and 18, including 2 protonated watermoleculeswere squeezed for compounds 1,2,and 3,respectively.Analytical expressions for neutral-atom scattering factors were employed,and anomalous dispersion corrections were incorporated.Details of the crystal parameters,data collection conditions,and refinement parameters for the three compounds are summarized in Table1.CCDC:1469246,1;1469247,2;1469248,3.Fig.2 shows the structure of compound 1.The supramolecular assembly is based on[ZnCl4]2-and [Zn(H2O)Cl3]-anions in which complexes of iQ[6]and Na+cations(Fig.2a)occupy the pores within the honeycomb-like framework constructed from[ZnCl4]2-and[Zn(H2O)Cl3]-anions(Fig.2b).Eachhollow in the honeycomb is occupied by one i Q[6]-Na+-based linear coordination polymer(Fig.2a,2c).Closer inspection of Fig.2a reveals that each i Q[6]molecule interactswith six Zn-based anions(four[ZnCl4]2-anions and two[Zn(H2O)Cl3]-anions)through ion-dipole interactions between Zn-based anions and the electropositive outer surface of i Q[6].The distance between chlorides from [ZnCl4]2-anions and methine or methylene carbons on the outer surface of i Q[6]ranged between 0.342 4 and 0.388 2 nm,and an additional hydrogen bond is present between a coordinated water molecule(O1W)bound to a[Zn(H2O)Cl3]-anion and a portal carbonyl oxygen (O8)of the i Q[6]-Na+complex,with a O1W-O8 distance of 0.270 5 nm(Fig.2d).Each i Q[6]molecule coordinates with four sodium cations,and each i Q[6] portal coordinates two Na1 and Na2 cations.Four carbonyloxygens(O11,O12 to Na1 and O8,O9 to Na2) form the top portal of i Q[6](Fig.2e),and both Na1 and Na2 cations coordinate with water molecules O2W, O3W and a carbonyl oxygen(O1)from a neighboring iQ[6]molecule.Furthermore,four carbonyl oxygens (O1,O2 to Na1 andO1,O6 to Na2)form the bottom portal of the i Q[6](Fig.2e),and again both Na1 and Na2 cations coordinate with water molecules O2W,O3W and a carbonyl oxygen(O1)from another neighboring i Q[6]molecule,with a Na+-portal carbonyl oxygen distanceof0.2286～0.261 7nm,and aNa+-Owaterdistance of 0.237 8～0.243 7 nm.Fig.3 showsstructureof compound 2.Fig.3a shows a similar supramolecular assembly,comprised of[ZnCl4]2-and[Zn(H2O)Cl3]-anions surrounded with i Q[6]moleculesand K+cationsby non-covalentinteraction.Again,the[ZnCl4]2-and[Zn(H2O)Cl3]-anions form a honeycomb-like framework(Fig.3b),and the i Q[6] -K+-based linear coordination polymers occupy the pores in this framework via outer surface interactions with the electropositive surface of Q[n](Fig.3a,c).Five [ZnCl4]2-anionsand three[Zn(H2O)Cl3]-anionssurround each i Q[6]molecule in the assembly,and close inspection reveals detailed interactions that include:(1)an ion-dipole interaction between a[ZnCl4]2-chloride and amethine ormethylene carbon from the outer surface of i Q[6],with a distanceof0.341 2～0.375 5 nm(dashed lines in Fig.3d);(2)an ion-dipole interaction between a[ZnCl4]2-chloride and an electron deficient carbonyl carbon with a distance of 0.327 6～0.336 2 nm(dashed lines in Fig.3d);(3)a hydrogen bond between a water molecule coordinated tothe[Zn(H2O)Cl3]-anion or K+cation and a portal carbonyl oxygen or chloride from the [Zn(H2O)Cl3]-anion,with a distance of 0.309 2～0.341 6 nm(dashed lines in Fig.3d).There is an additional interaction between a coordinated K+cation(K4)and a[ZnCl4]2-anion,with K-Cl distances of 0.325 9 and 0.328 9 nm,respectively(Fig.3d).Each i Q[6]in compound 2 is also coordinated to four K+cations(K1 and K2 from one portal,and K3 and K4 from the other portal.K1 coordinates to eight oxygen atoms,two carbonyl oxygens(O1,O2),and six watermolecules (O4W,O5W,O6W,O7W,O10W and O11W);K2 coordinates to seven oxygen atoms,fourcarbonyloxygens(O3,O4,and O13,O14 from a neighbouring iQ[6]molecule),and three water molecules(O9W, O8W and O7W);K3 coordinates only to three carbonyl oxygens(O7,O12 and O21 from anotherneighbouring i Q[6]molecule);K4 coordinates only to two carbonyl oxygens(O11 and O21 from another neighbouring i Q[6]molecule).Distances between K+and portal carbonyl oxygens are in the range of 0.232 2～0.321 2 nm,and K+-Owaterdistances are 0.236 2～0.297 4 nm.Compound 3hasasimilarsupramolecularassembly to 1 and 2 described above,in which[ZnCl4]2-and [Zn(H2O)Cl3]-anions form ahoneycomb-like framework, and i Q[6]molecules coordinated with Rb+cations form a linear coordination polymer that is inserted in the cells of the framework(Fig.4a～c).Each i Q[6]molecule is surrounded by three[ZnCl4]2-anions and three [Zn(H2O)Cl3]-anions through ion-dipole interactions between a[ZnCl4]2-chlorideand amethineormethylene carbon on the outer surface of iQ[6],with a distance of0.338 1～0.371 2 nm(Fig.4d).An additionalhydrogen bond is present between watermolecule(O1W)coordinated tothe[Zn(H2O)Cl3]-anion and portal carbonyl oxygen(O9),with a distance of 0.268 3 nm(dashed lines in Fig.4d).Each i Q[6]is also coordinated to rubidium cation Rb1 at both portals.Rb1 coordinates to five oxygen atoms(carbonyl oxygensO1,O2 and O10 and O11 from a neighboring iQ[6]),and one water molecule(O2W).The Rb+-portal carbonyl oxygen distance is 0.278 4～0.301 9 nm,and the K+-Owaterdistance is 0.305 6nm(Fig.4e).The crystal structures therefore revealed a similar Zn-based honeycomb-like framework filled with linear i Q[6]/M+-based coordination polymers for all three compounds(Fig.2a,3a,4a).However,closer inspection revealed aslightly different arrangement of the linear i Q[6]/M+-based coordination polymers that led to different porous supramolecular assemblies with different alkali metal ions.With Na+(compound 1),i Q[6]/Na+-based coordination polymers are arranged tightly, with noobvious free space.In contrast,with K+and Rb+(compounds2and 3,respectively),the zigzag-like i Q[6]/ K+and Rb+-based coordination polymersare arranged into different porous assemblies(Fig.5).In the present study,we discovered that iQ[6] forms linear coordination polymers with alkali metal ions(M+)in the presence of[ZnCl4]2-anion structuredirecting agents.The supramolecular assemblies consist ofa[ZnCl4]2-based honeycomb-like framework that interacts with the electropositive outer surface of i Q[6]through ion-dipole interactions.The electronegative environment presumably attracts the M+cations to the portals of i Q[6],resulting in their coordination and formation of the 1D coordination polymers.Interestingly,different M+cations resulted in the formation of different supramolecular assemblies with different structural features.In particular the pore size was dependent on the ionic diameter of the cation.The resultant supramolecular assembliesmight give rise to different absorption characteristics,and furtherinvestigation is underway in our laboratory.Acknowledgments:Weacknowledge the supportofNational Natural Science Foundation of China(Grant No.21272045, 21561007).References:[1]Isaacs L,Park SK,Liu SM,etal.J.Am.Chem.Soc.,2005, 127:18000-18001[2]Isaacs LD,Liu SM,Kim K,etal.WO Patent,2007014214-A2.2007-02-01.[3]PinjariR V,GejjiSP.J.Phys.Chem.A,2009,113:1368-1376[4]Raja IA,Gobre V V,Pinjari R V,etal.J.Mol.Model.,2014, 20:1-7[5]Zhang D Q,Lin R L,Sun W Q,et .Biomol.Chem., 2015,13:8330-8334[6]Zhang D Q,Sun T,Zhang Y Q,et al.Eur.J.Inorg.Chem., 2015,2:318-323[7]Zhang D Q,Zhang Y Q,Xue SF,et al.Polyhedron,2015,99: 147-155[8]Ni X L,Xiao X,Cong H,et al.Chem.Soc.Rev.,2013,42: 9480-9508[9]NiX L,Xue S F,Tao Z,etal.Coord.Chem.Rev.,2015,287: 89-113[10]Ni X L,Xiao X,Cong H,et al.Acc.Chem.Res.,2014,47: 1386-1395[11]SAINT,Program for Data Extraction and Reduction,BrukerAXS,Inc.,Madison,WI,2001.[12]Sheldric k GM.SADABS,University of Göttingen,Germany, 1996.[13]Sheldrick GM.ActaCrystallogr.Sect.A,2008,A64:112-122[14]Sheldrick G M.SHELXL-97,Program for the Solution and Refinement of Crystal Structures,University of Göttingen, Germany,1997.[15]Spek A L.Acta Crystallogr.Sect.A,1990,A46:194-201。

六元瓜环与[Zn(H2O)6] 2+的超分子自组装结构

为３９１，其中独立衍射点为６０个。强度数据进行了经验吸收校正、Ｌ校正。结构解析用ＳＲ９６２个０６ＰＩ－２
程序，结构修正用ＳＥＸ－程序，氢原子坐标由差值Ｆｕｅ合成法得到，最后一轮最小二乘法精修ＨＬＬ９７ｏｒｒｉ
用４３８６个可观察点（ｓＩ）Ｉ（）修正４４个可变参数。晶体数据和结构修正参数见表１２８。
ＪｕａｏｕｚｏｎｖｒｉＮｔｒｃｅｃｓｏｒｌｆｉｕＵｉｅｓｙ（ａａＳｉｎｅ）ｎＧｈｔｕｌ
Ｖ０．２．３１４Ｎｏ
Ｍａ．２０ｙ０７
文章编号
１０００—５６（０７００００２９２０）３— ３６— ３
六元瓜环与［ｎ（６２ＺＨ２ｏ）］＋的超分子自组装结构
２结果讨论
虽然瓜环具有偶极化的端口羰基氧原子，可能与金属离子或有机阳离子发生相互作用，但实验结果
收稿日期：０７－３— ６２００２。
作者简介：张云黔，男，副教授；研究方向：晶体结构解析。
维普资讯
聚轮烷实体［］５。这些研究结果预示，瓜环在晶态结构定向组装应用方面具有独特的开发潜力。
本文合成了Ｑ６与ｚ（Ｉ离子形成的自组装配合物，［］ｎＩ）并测定了它的晶体结构。在其结构中，瓜环分子包结一个１４二氧六烷分子，并与瓜环两端的锌水合离子发生端口作用形成分子胶囊结构，瓜环胶，囊间通过ｚ（Ｉ离子的水合物与瓜环端口羰基氧原子形成的氢键连接而成一维自组装超分子链。ｎＩ）

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２１００年ｌ０月第３期
兴义民族师范学院学报
ＪｕｎｌｏＸｉｇｉＮｏｍａＵｎｖｒｉｆｒＮａｉｎｌｉｓｏｒａｆｎｙｒｌｉｅｓｔｙｏｔａｉｅｏｔ
０ｃ．２１ｔ００
Ｎｏ３．
对称四甲基六元瓜环与Ｃ（Ｉ生成的自组装超分ａ１）子配合物的晶体结构
ｂｌｇｉｌｉｓｓｍｗｔｓａｅｒｕ－，＝１４４（７ｎｂ＝１９４２ｎ，＝１１２２ｎ仅＝６．９２。，＝ｅｎｓｏｒｉｃｙｔｉｃｏｐＰ１ａ．５０１）ｍ，ｏｔｔｃｎｅｈｐｇ０．１（）ｍｃ．７（ｍ，２５）５４（５）Ｂ
Ｔｔｍｅｈｌｓｂｔｕｅｃｒｉ６ｕｉｔｌｕＣｈｏｉｅｅｒａｔｙｕｓｉｔｄＣｕｕｂｔ】ｈＣａｃｍｌｒ — ｔ【ｒｗｉｌｉｄ
ＣＨＥＮｎ－ｕＭｉｇｈａ
（ｉｇｉｏｍａＵｉｒｔｒａｏａｔｓＸｎｙＧｉｏ６４０，ｈｎ）ＸｎｙＮｒｌｎｖｓｙｏＮｔｎｌｉ，ｉｇｉｕｚｕ５２０Ｃｉａｅｉｆｉｉｅ，ｈ
７．２（。，＝７．７２。，＝１５９ｎ，３５１）２３４（９）Ｖ．３５ｍ一Ｚ＝１Ｄ＝１４ｇｃ＝０４９一ｖｏｏ＝８２ＴｅｎｌＲ＝００１，７，ｃ．０。ｍ，５．１ｍｍ，（ｏ）３．ａｈｆｉ．６６
ｗＲ＝０．９８１６．
ＫｙｗｒｓＴｔｍｔｙ－ｕｓｔｔｕｕｂｔ］ｒ；ｕｒｌｕａ；ｅ－ｓｅｂｙＣｙｔｌｔｃｕｅｅｏｄ：ｅａｅｌｓｂｔｕｅｃｃｒｉ６ｕｉＳｐａｅｌＳｌａｓｍｌ；ｒｓｒｔｒｓｒｈｉｄ［ｌｍｏｃｒｆａＳｕ
ＡｓｒｃＡｓｐａｏｅｕａｌａｓｍｂｏｐｅｅｔｍｔｙｓｂｔｕｅｕｕｂｔ］ｒｉａｉｍＣｌｄａｂｔ：ｒｍｌｅｌｓｆｓｅｌｃｍｌｓｆｅｒｅｌｕｓｔｄＣｃｒｉ６ｕｉｗｔＣｌｕｈｏｅｓａｕｒｅ－ｙｘｏｔａｈ－ｉｔ［ｌｈｃｉｒＷ
超分子化学或主客体化学是关于两个或两个以上的化学物种通过分子间作用力缔合在一起而
形成的具有更高复杂性的有组织实体口分子间的ｌ。作用力包括氢键、范德华力、偶极／偶极相互作用、亲水／疏水相互作用等。在主客体化学中，人们对冠醚、环糊精和杯芳烃等主体与不同客体做
关键词：称四甲基六元瓜环；对超分子；自组装；晶体结构
文章编号：０９－０７（００－０７－４１０－６３２１３１－－－０）００
中图分类号：２．３０６６２
文献标识码：Ｂ
ＣｒｓａｒｃｕｅｆｌａｓｍｂｙＳｕｒｍｏｅ－ｌｐａｌｃｌＣｏｌｘｓＯ
物一瓜环（葫芦脲，ｕｕｂ［ｕｉｎ５６７８的Ｃｃｒｉｎｒ，＝，，，）ｔ］ｌ发现，以瓜环为主体的超分子化学成为研究的一
个重要热点［］２。－５
瓜环是以苷脲单元通过亚甲基桥联结成的一系列具有疏水空腔的大环化合物，目前已报道的有五、、、六七八及十元瓜环［］６。－相对于其他超分子８
ｓｎｈｓｚｄｉｑｅｕｏｕｉｎＴｅｅｐｒｎａｓｌｏｒｙｓｎｌｒｓａｉｒｃｉｎａａｙｉｖａｅａｅｔｅｃｍｐｕｄｙｔｅｉｅａｕｏｓｌｔ．ｈｘｅｉｎｓｏｍｅｔｌｅｕｔｆｒＸ－ａｉｇｅｃｙｔｌｄｆａｔｎｓｓｅｅｌｄｔｔｈｄｏｏｎｏｌｒｈｔｉ
陈明华
（义民族师范学院，贵州兴义５２０）兴６４０
摘要：以对称四甲基六元瓜环（Ｍｅ６）ＣＣ２ＴＱ【和ａ１在水溶液中生成了标题化合物并得到其单晶。】
ｘ一射线单晶衍射测试得到的晶体数据：斜晶系，间群：一１ａ；１０５０１）ｍ，单空Ｐ，．４４（ｎｂ：１９４２ｎｃ７．１（ｍ，２）
＝１５７（）ｎ，．１２２／＇Ｉ＝６．５（。，１：７．１（。，＾７．７（），＝１７３５ｍＺ＝１Ｄｃ＝５４９２）３３２２５）ｙ＝３４９２。Ｖ．５９ｎ，，
１５０・ｍ＝０４９ｍｍ一ＦＯ０＝８２最终偏离因子Ｒ＝００１，．４ｇｃ，．１，（）３．０．６ｗＲ＝０１８．６．６９