Assembly of high nuclearity clusters from a family of tripodal tris-carboxylate ligands
Assembly of high nuclearity clusters from a family of tripodal tris-carboxylate ligands
复制标题
DOI：
10.1016/j.poly.2016.04.029
复制
发表时间：
2016-12-14
期刊：
影响因子：
2.6
通讯作者：
Blake, Alexander J.
中科院分区：
文献类型：
--
作者：
Argent, Stephen P.;Tarassova, Irina;Blake, Alexander J.
一族四个三羧酸配体1，3，5-tris（4 '-羧基联苯-2-基）苯（H3 L1）、1，3，5-三-2-羧基苯基苯（H3 L2）、1，3，5-三（4“-羧基-对-三联苯-2-基）苯（H3 L3）和1，3，5-三（3 '-羧基联苯-2-基）苯（H3 L4）已经合成并与第一行过渡金属阳离子反应，得到九个配合物，其结构特征在于通过X-射线晶体学。配体共享共同的设计基序，其具有经由三个邻位二取代的苯基接头连接至苯核的三个臂。配体在羧酸官能化臂的长度和方向上变化，并且都能够采用三足构象，其中三个臂面向表面。[ZnS（mu（4）-O）（L-1）（4）（HCO_2）（2）（H_2 O）]配合物的结构（0.33）（DMF）（2）]（1a-Zn），[Co-14（L-2）（6）（（mu（3）-OH）（8）（HCO2）（2）（DMF）（4）（H2O）（6）]（2-Co），[Ni-14（L-2）（6）（mu（3）-OH）（8）（HCO2）（2）（DMF）（4）（H2O）（6）]（2-Ni），[Zn-8（mu（4）-0）（L-3）（4）（DMF）（H2O）（4）（NO3）（2）]（3-Zn），[Ni-5（mu-OH）（4）（L-2）（2）（H2O）（6）（DMF）（4）]（5-Ni），[Co-8（mu（4）-O）（4）（L-4）（4）（DMF）（3）（H2O）]（6-Co）和Fe-3（mu（3）-O）（L-4）（2）（H2O）（DMF）（2））]（7-Fe）含有三足构型的配体（L1-4）（3-）包围的多核簇。[Zn-2（HL 1）（2）（DMF）（4）]（1b-Zn）是一个双核配合物，其中两个配体（HE 2）（2-）部分去质子化，而{[Zn-3（L-2）（2）（DMF）（H2O）（C5 H5 N）]中心点6（DMF）}（n）（4-Zn）是一个含有（Zn-2（RCO 2）（4）（solv）（2））桨轮单元的二维配位网络。配合物中的配体臂的构象进行了分析，证实了共享的邻位二取代的苯环基序是一个强大的和通用的工具，用于设计配体，能够形成高核度的配位簇时，与过渡金属阳离子反应。(C)2016爱思唯尔有限公司版权所有
A family of four tris-carboxylic acid ligands 1,3,5-tris(4'-carboxybiphenyl-2-yl)benzene (H3L1), 1,3,5-tris-2-carboxyphenylbenzene (H3L2), 1,3,5-tris(4 ''-carboxy-para-terphenyl-2-yl)benzene (H3L3) and 1,3,5-tris(3'-carboxybiphenyl-2-yl)benzene (H3L4) have been synthesised and reacted with first row transition metal cations to give nine complexes which have been structurally characterised by X-ray crystallography. The ligands share a common design motif having three arms connected to a benzene core via three ortho-disubstituted phenyl linkers. The ligands vary in length and direction of the carboxylic acid functionalised arms and are all able to adopt tripodal conformations in which the three arms are directed facially. The structures of [Zns(mu(4)-O)(L-1)(4)(HCO2)(2)(H2O)(0.33)(DMF)(2)] (1a-Zn), [Co-14(L-2)(6) ((mu(3)-OH)(8)(HCO2)(2)(DMF)(4)(H2O)(6)] (2-Co), [Ni-14(L-2)(6)(mu(3)-OH)(8)(HCO2)(2)(DMF)(4)(H2O)(6)] (2-Ni), [Zn-8(mu(4)-0) (L-3)(4)(DMF)(H2O)(4)(NO3)(2)] (3-Zn), [Ni-5(mu-OH)(4)(L-2)(2)(H2O)(6)(DMF)(4)] (5-Ni), [Co-8(mu(4)-O)(4)(L-4)(4)(DMF)(3)(H2O)] (6-Co) and Fe-3(mu(3)-O)(L-4)(2)(H2O)(DMF)(2))] (7-Fe) contain polynuclear clusters surrounded by ligands (L1-4)(3-) in tripodal conformations. The structure of [Zn-2(HL1)(2)(DMF)(4)] (1b-Zn) shows it to be a binuclear complex in which the two ligands (HE2)(2-) are partially deprotonated whilst {[Zn-3(L-2)(2)(DMF)(H2O) (C5H5N)]center dot 6(DMF)}(n) (4-Zn) is a 2D coordination network containing (Zn-2(RCO2)(4)(solv)(2)) paddlewheel units. The conformations of the ligand arms in the complexes have been analysed, confirming that the shared ortho-disubstituted phenyl ring motif is a powerful and versatile tool for designing ligands able to form high-nuclearity coordination clusters when reacted with transition metal cations. (C) 2016 Elsevier Ltd. All rights reserved.