Lippi Martina, Caputo Josefina, Meneghetti Fiorella, Castellano Carlo, Martí-Rujas Javier, Cametti Massimo
Dipartimento di Chimica, Materiali e Ingegneria Chimica, Politecnico di Milano, Via Luigi Mancinelli, 7, 20131, Milano, Italy.
Dalton Trans. 2020 Oct 6;49(38):13420-13429. doi: 10.1039/d0dt02734k.
Here we report novel bispidine-based coordination polymers (CPs) 2·TCM, 3·TCM, 3·NB, 5·TCM and 5·TCM·NB, of compostition [Mn(Cl)2(L2)2·(TCM)2], [Mn(Cl)2(L3)2·(TCM)5], [Mn(Cl)2(L3)2·(NB)8], [Mn(Cl)2(L5)2·(TCM)4], [Mn(Cl)2(L5)2·(TCM)2·(NB)2], respectively (NB = nitrobenzene; TCM = chloroform). They were obtained starting from novel bispidine ligands L2 (dimethyl 7-isopropyl-3-methyl-9-oxo-2,4-di(pyridin-4-yl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate), L3 (dimethyl 7-(cyclohexylmethyl)-3-methyl-9-oxo-2,4-di(pyridin-4-yl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate) and L5 (dimethyl 7-(4-(dimethylamino)benzyl)-3-methyl-9-oxo-2,4-di(pyridin-4-yl)-3,7-diazabicyclo[3.3.1]nonane-1,5-dicarboxylate), The novel CPs were characterized by single crystal X-ray diffraction (SC-XRD), powder X-ray diffraction (PXRD) and thermal analyses (TGA). We describe their structural and dynamic properties in terms of solvent exchange and adsorption processes, and we outline the general trends observed on the basis of a total of 16 X-ray structures (4 new) and 21 microcrystalline powder phases (10 new), which have been obtained so far for CPs by coordination of ligands L1-L5, having different substitution at the N7 position. This large set of CPs comprises monosolvated, bisolvated and desolvated species, and it shows a good demonstration of how small differences in the functionalization of the organic ligand can have a strong impact on the resulting structural and dynamic properties of this class of 1D CPs.
在此，我们报道了新型的基于联吡啶的配位聚合物（CPs）2·TCM、3·TCM、3·NB、5·TCM和5·TCM·NB，其组成分别为[Mn(Cl)2(L2)2·(TCM)2]、[Mn(Cl)2(L3)2·(TCM)5]、[Mn(Cl)2(L3)2·(NB)8]、[Mn(Cl)2(L5)2·(TCM)4]、[Mn(Cl)2(L5)2·(TCM)2·(NB)2]（NB = 硝基苯；TCM = 氯仿）。它们是从新型联吡啶配体L2（7-异丙基-3-甲基-9-氧代-2,4-二（吡啶-4-基）-3,7-二氮杂双环[3.3.1]壬烷-1,5-二甲酸二甲酯）、L3（7-（环己基甲基）-3-甲基-9-氧代-2,4-二（吡啶-4-基）-3,7-二氮杂双环[3.3.1]壬烷-1,5-二甲酸二甲酯）和L5（7-（4-（二甲氨基）苄基）-3-甲基-9-氧代-2,4-二（吡啶-4-基）-3,7-二氮杂双环[3.3.1]壬烷-1,5-二甲酸二甲酯）出发制得的。这些新型配位聚合物通过单晶X射线衍射（SC-XRD）、粉末X射线衍射（PXRD）和热分析（TGA）进行了表征。我们从溶剂交换和吸附过程的角度描述了它们的结构和动态性质，并根据总共16个X射线结构（4个新结构）和21个微晶粉末相（10个新相）概述了观察到的一般趋势，这些结构和相是通过配体L1 - L5的配位作用得到的，L1 - L5在N7位置具有不同的取代基。这一大组配位聚合物包括单溶剂化、双溶剂化和去溶剂化的物种，很好地证明了有机配体功能化的微小差异如何对这类一维配位聚合物的结构和动态性质产生强烈影响。
