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Tuneable solvent adsorption and exchange by 1D bispidine-based Mn(II) coordination polymers via ligand design.
Dalton Transactions ( IF 3.5 ) Pub Date : 2020-08-31 , DOI: 10.1039/d0dt02734k
Martina Lippi 1 , Josefina Caputo , Fiorella Meneghetti , Carlo Castellano , Javier Martí-Rujas , Massimo Cametti
Affiliation  

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.

中文翻译:

可调谐溶剂的吸附和一维双联吡啶基Mn(II)配位聚合物通过配体设计的交换。

在这里,我们报告了新型堆肥[Mn(Cl)2L22 ·(TCM)的双联吡啶基配位聚合物(CPs)2·TCM3·TCM3·NB5·TCM5·TCM·NB 2 ],[Mn(Cl)2L32 ·(TCM)5 ],[Mn(Cl)2L32 ·(NB)8 ],[Mn(Cl)2L52 ·(TCM )4 ],[Mn(Cl)2L52·(TCM)2 ·(NB)2 ]分别(NB =硝基苯; TCM =氯仿)。它们是从新颖的双联吡啶配体L2(二甲基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, 5-二羧酸盐),L3(二甲基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 -二羧酸盐)和L5(二甲基7-(4-(二甲基氨基)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-通过单晶X射线衍射(SC-XRD),粉末X射线衍射(PXRD)和热分析(TGA)对新型CP进行表征。我们根据溶剂交换和吸附过程描述了它们的结构和动力学性质,并根据总共16个X射线结构(4个新的)和21个微晶粉末相(10个新的)概述了观察到的总体趋势。到目前为止,通过配体L1-L5的配位已获得CP的化合物,在N7位置具有不同的取代。大量的CP包含单溶剂,双溶剂和去溶剂的物质,它很好地证明了有机配体官能化的微小差异如何对此类一维CP的结构和动力学性质产生强烈影响。
更新日期:2020-10-06
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