Béziau Antoine, Baudron Stéphane A, Rogez Guillaume, Hosseini Mir Wais
Laboratoire de Tectonique Moléculaire, UMR UdS-CNRS 7140, icFRC, Université de Strasbourg , 4 Rue Blaise Pascal, F-67000, Strasbourg, France.
Inorg Chem. 2015 Feb 16;54(4):2032-9. doi: 10.1021/ic502950k. Epub 2015 Jan 26.
A strategy for the conversion of homometallic coordination networks into mixed metal-organic frameworks (MM'MOFs) is proposed. Ni(II) complexes of dipyrrin (dpm) ligands bearing peripheral pyridyl or imidazolyl units have been shown to self-assemble into coordination polymers with the metal cation in an octahedral environment coordinated to two bis-pyrrolic chelates and two neutral monodentate coordinating units such as pyridyl or imidazolyl moieties. Taking advantage of the chelate effect, the two monodentate units may be replaced by a diimine ligand leading to the disassembly of the networks by the formation of discrete soluble complexes. The latter can be employed as metallatectons for the construction of heterometallic architectures upon reaction with a secondary metal salt. This approach was applied using either 1,10-phenanthroline (phen) or 2,2'-bipyrimidine (bpm) as chelates leading to a series of mono- and binuclear metallatectons of the (phen)Ni(dpm)2 and (bpm)[Ni(dpm)2]2 type. Subsequent assembly with CdCl2 afforded either interpenetrated 2D grid-type architectures or 3D MM'MOFs.
提出了一种将同金属配位网络转化为混合金属有机框架（MM'MOFs）的策略。带有外围吡啶基或咪唑基单元的二吡咯（dpm）配体的Ni（II）配合物已被证明能在八面体环境中与金属阳离子自组装成配位聚合物，其中金属阳离子与两个双吡咯螯合物以及两个中性单齿配位单元（如吡啶基或咪唑基部分）配位。利用螯合效应，两个单齿单元可以被二亚胺配体取代，通过形成离散的可溶性配合物导致网络解体。后者可以用作金属构筑单元，在与二级金属盐反应时用于构建异金属结构。使用1,10 - 菲咯啉（phen）或2,2'-联嘧啶（bpm）作为螯合物应用了这种方法，得到了一系列（phen）Ni（dpm）2和（bpm）[Ni（dpm）2]2类型的单核和双核金属构筑单元。随后与CdCl2组装得到了互穿的二维网格型结构或三维MM'MOFs。
