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首页> 外文期刊>Chemistry: A European journal >A cuboctahedral supramolecular capsule by 4:4 self-assembly of tris(Zn~(II)-cyclen)and trianionic trithiocyanurate in a queous solution at neutral pH(cyclen=1,4,7,10-tetraazacyclododecane)
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A cuboctahedral supramolecular capsule by 4:4 self-assembly of tris(Zn~(II)-cyclen)and trianionic trithiocyanurate in a queous solution at neutral pH(cyclen=1,4,7,10-tetraazacyclododecane)

机译：三（Zn〜（II）-cycln）和三阴离子三硫氰脲酸酯在水溶液中性pH下4：4自组装的立方八面体超分子胶囊（周期数= 1,4,7,10-四氮杂环十二烷）

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A 1:1 mixture of a tris(Zn~#mu#-cyclen)(1:[Zn_3L~1],L~1=1,3,5-trisyl)benzene and trithiocyanuric acid (TCA)yielded a 4:4 self-assembly complex [Zn_3L~1]_4-[TCA~(3-)_4] (6)through the formation of Zn~(II)-S~- coordination bonds and hydrogen bonds between 1,3,5-trazine N and cyclen NH (cyclen=1,4,7,10-tetraazacyclododecane); the supramolecular capsule structure was revealed by X-ray crystal structure analysis.The capsule exterior represents a twisted cuboctahedral framework containing a nanoscale truncated tetrahedral cavity.The crystal data:for-mula C_(144)H_(308)N_(72)O_(58)S_(12)Zn_(12) (6[NO_3]_(12).22H_2O),Mr=5145.75, cubic,space group F432 (No.209),a=39.183(1) A,V=60153(3) A~3,Z=8,R=0.100.R_w=0.259.Lipophilic organic molecules with the matching sizes,for example,([D_4]-2,2,3,3)-3-(trimethylsilyl)propionic acid (TSP),1-adamantanecarboxylic acid,2,4-dinitrophenol (2,4-DNP),adamantane (ADM),or the tetra-n-propylammonium (TPA) cation,are encapsulated inthe inner cavity,as revealed by remarkable upfield shifts of the ~1H NMR signals of these guest molecules.The encapsulation of ADM was confirmed by X-ray crystal data of the ADM-encapsulating complex:formula C_(154)H_(334)N_(72)O_(63)S_(12)Zn_(12) (6-ADM[NO_3]_(12) centre dot 27H_2O),M_r=5372.06,cubic,space group F432(No.209),a=39.061(1) A, V=59599(3) A~3,Z=8,R=0.103,R_w=0.263.The incorporation of one of these guestnolecules.The apparent 4:4 self-assembly constants for 6 in the presence of an excess amount of a guest TPA,logK_(app) (K_(app)=[6-TPA]/[1]~4[TCA]~4)(M~(-7)),were determined to be 34.0+-2.0 and 35.5+-3.0 by potentiomertric pH and UV spectrophotometric titrations,respectively.Anapparentencapsulation constant for 2,4-DNP,logK_(enc)(K+(enc)=[6-2,4-DNP]/[6][2,4-DNP](M~(-1)),was 6.0+-0.1 at pH7.0 (50mM HEPES with I=0.1(NaNO_3)),as determined by UV titrations.The lipophilicity oftheinner cavity was close to that of 2-propanol,as quantum yield (#psi#) of 0.24+-0.1 for the fluorescent emission of 7-diethylaminocoumarin-1-carboxylic acid (20#mu#m)in the capsule was close to the #psi# of 0.22 found for 2-propanol.Encapsulation cage have been compared with those of cyclodextrins and Fujita's Pd~(II)-containing supramolecular cage.The exterior chirality of the 4:4 complex was controlled from within by an encapsulated chiral guest molecule,2,10-camphorsultam,as indicated by Cotton effects in the circular dichroism spectra.
机译：三（Zn〜＃mu＃-cycln）（1：[Zn_3L〜1]，L〜1 = 1,3,5-三甲苯基）苯和三硫氰尿酸（TCA）的1：1混合物产生4：4自组装复合物[Zn_3L〜1] _4- [TCA〜（3-）_ 4]（6）通过形成Zn〜（II）-S〜-配位键和1,3,5-三嗪N之间的氢键和循环NH（循环= 1,4,7,10-四氮杂环十二烷）;通过X射线晶体结构分析揭示了超分子胶囊的结构。胶囊的外部代表扭曲的立方八面体骨架，其中包含纳米级的截短的四面体空腔。晶体数据：分子式C_（144）H_（308）N_（72）O_（ 58）S_（12）Zn_（12）（6 [NO_3] _（12）.22H_2O），Mr = 5145.75，三次空间群F432（No.209），a = 39.183（1）A，V = 60153（ 3）A〜3，Z = 8，R = 0.100.R_w = 0.259。具有匹配大小的亲脂性有机分子，例如（[D_4] -2,2,3,3）-3-（三甲基甲硅烷基）丙酸（TSP），1-金刚烷羧酸，2,4-二硝基苯酚（2,4-DNP），金刚烷（ADM）或四正丙基铵（TPA）阳离子被包裹在内腔中，这是由显着的高场显示的这些客体分子的〜1H NMR信号发生了位移.ADM的包封由ADM包封复合物的X射线晶体数据证实：分子式C_（154）H_（334）N_（72）O_（63）S_（ 12）Zn_（12）（6-ADM [NO_3] _（12）中心点27H_2O），M_r = 5372.06，三次，空间群F432（No.209），a = 39.061（1）A，V = 59599（3 ）A〜3， Z = 8，R = 0.103，R_w = 0.263。这些客体分子之一的掺入。在客体TPA过量时存在6的表观4：4自组装常数logK_（app）（K_（ app）= [6-TPA] / [1]〜4 [TCA]〜4）（M〜（-7）），通过电位滴定pH和紫外分光光度法滴定确定为34.0 + -2.0和35.5 + -3.0， 2,4-DNP的表观包封常数，logK_（enc）（K +（enc）= [6-2,4-DNP] / [6] [2,4-DNP]（M〜（-1）），通过UV滴定法测定，在pH7.0（50mM HEPES，I = 0.1（NaNO_3））下为6.0 + -0.1。内腔的亲脂性接近2-丙醇，量子产率（＃psi＃）为0.24胶囊中7-二乙基氨基香豆素-1-羧酸（20＃mu＃m）的荧光发射值为+ -0.1，与2-丙醇的＃psi＃为0.22接近。已将封装笼与环糊精进行了比较包封的手性客体分子从内部控制了4：4配合物的外部手性e，2,10-camphorsultam，如圆二色光谱中的棉花效应所示。

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