芳香碘基辅助的配位超分子自组装——锌(II)、镉(II)与7-碘-8-羟基喹啉-5-磺酸配合物的合成和结构  

Aromatic Iodine Assisted Self-assembly of Zn(II) and Cd(II) Complexes of 7-Iodo-8-hydroxyquinoline-5-sulfonate

作　　者：张锋[1] 桑石云[1] 张阳阳[1] 张向东[1] 李一志[2] 陈慧兰[2] 刘祁涛[1] 

机构地区：[1]辽宁大学化学科学与工程学院,沈阳110036 [2]南京大学配位化学国家重点实验室,南京210093

出　　处：《化学学报》2004年第20期2055-2061,F009,共8页Acta Chimica Sinica

基　　金：国家自然科学基金 (No.2 9971 0 1 4 );教育部归国博士启动基金 (1 998[679] );辽宁省科委自然科学基金 (No.991 0 50 0 50 6)资助项目

摘　　要：合成了锌 (II)、镉 (II)与 7 碘 8 羟基喹啉 5 磺酸 (IHQS)的两种单晶配合物 [Zn(IHQS) (H2 O) 3 ] 2 ·4H2 O ( 1)和 [Cd (IHQS) (H2 O) 2 ] n·2nH2 O ( 2 ) ,用X射线衍射法确定了结构 .结果表明 ,1和 2均由一对对映体配合物构成 :1中两个 [Zn (IHQS) (H2 O) 3 ]对映体通过磺酸基 -锌 (II)八面体轴向互补配位形成中心对称双分子聚合体 ,该聚合体通过分子间磺酸基氧 -配位水氢键形成独特的二维层状结构 ;2的两个 [Cd(IHQS) (H2 O) 2 ]对映体通过镉 (II) 磺酸基 -镉 (II)双向互补配位形成一维直线型聚合配位结构 .芳香碘基呈现新颖的碘 -芳环氢和碘 -磺酸基氧等弱相互作用模式 ,并对上述结构的支撑稳定发挥重要的结构辅助作用 .本文展示了芳香碘基、磺酸基和喹啉环三种弱相互作用基团在配位超分子自组装中的形状、空间匹配和协同促进模式 .结晶学参数配合物 1:单斜晶系 ,C2 /c空间群 ,a =2 2 2 43 ( 7)nm ,b =1 0 0 5 3 ( 3 )nm ,c =1 3 468( 4 )nm ,β =10 2 2 67( 5 )° ,V =2 942 8( 16)nm3 和Z =4.配合物 2 :三斜晶系 ,P1- 空间群 ,a =0 6949( 2 )nm ,b =1 0 183 ( 3 )nm ,c =1 0 989( 3 )nm ,α =76 0 69( 5 )° ,β =75 2 94( 5 )° ,γ =84 747( 5 )° ,V =0 72 95 ( 4 )nm3 和Z =2 .Two complexes [Zn(IHQS)(H_2O)_3]_2·4H_2O (1) and [Cd(IHQS)(H_2O)_2]_n·2nH_2O (2) (IHQS=7-iodo-8-hydroxyquinoline-5-sulfonate) have been synthesized and investigated by X-ray diffraction method. Both 1 and 2 are composed of a pair of coordination enantiomers. Compound 1 exhibits a coupled dimer coordination of the [Zn^(IHQS)(H_2O)_3] enantiomer pair by a complementary sulfonato-coordination to the octahedral Zn(II) centers, and the dimer further forms a unique 2D-layer structure by double hydrogen interactions between the sulfonato group and the coordination water molecule. Compound 2 has a linear 1D-coordination polymer structure, which is formed by the [Cd^(IHQS)(H_2O)_3] enantiomer pair through a bis-complementary sulfonato-coordination mode. The aromatic iodo group demonstrated novel C—I…H (quinoline ring) and C—I…O (sulfonate) weak interactions, which are important for supporting these structures. The results provided an interesting example of the molecular shape-fitting and space-matching weak interactions involving the iodo, sulfonato, and quinoline moieties. Compound 1 is in monoclinic C2/c space group with a=2.2243(7) nm, b=1.0053(3) nm, c=1.3468(4) nm, β=102.267(5)°, V=2.9428(16) nm^3, and Z=4. Compound 2 is in triclinic P1- space group with a=0.6949(2) nm, b=1.0183(3) nm, c=1.0989(3) nm, α=76.069(5)°, β=75.294(5)°, γ=84.747(5)°, V=0.7295(4) nm^3 and Z=2.

关 键 词：超分子 自组装 7-碘-8-羟基喹啉-5-磺酸 锌配合物 镉配合物 合成 晶体结构 分子识别 

分 类 号：O621[理学—有机化学]