二维配位层通过配位聚合物中的 B-H···Cu(II) 相互作用发生的可逆相转变。

A Reversible Phase Transition of 2D Coordination Layers by B-H∙∙∙Cu(II) Interactions in a Coordination Polymer.

机构信息

Institut de Ciència de Materials de Barcelona (ICMAB-CSIC), 08193 Bellaterra, Spain.

Department of Chemistry, University of Southampton, Highfield, Southampton SO17 1BJ, UK.

出版信息

Molecules. 2019 Sep 3;24(17):3204. doi: 10.3390/molecules24173204.

DOI:10.3390/molecules24173204

PMID:31484428

原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC6751501/

Abstract

Materials that combine flexibility and open metal sites are crucial for myriad applications. In this article, we report a 2D coordination polymer (CP) assembled from CuII ions and a flexible -carborane-based linker [Cu(L1)(Solv)]•xSolv (1-DMA, 1-DMF, and 1-MeOH; L1: 1,7-di(4-carboxyphenyl)-1,7-dicarba-closo-dodecaborane). 1-DMF undergoes an unusual example of reversible phase transition on solvent treatment (i.e., MeOH and CHCl). Solvent exchange, followed by thermal activation provided a new porous phase that exhibits an estimated Brunauer-Emmett-Teller (BET) surface area of 301 m g and is capable of a CO uptake of 41 cm g. The transformation is reversible and 1-DMF is reformed on addition of DMF to the porous phase. We provide evidence for the reversible process being the result of the formation/cleavage of weak but attractive B-H∙∙∙Cu interactions by a combination of single-crystal (SCXRD), powder (PXRD) X-ray diffraction, Raman spectroscopy, and DFT calculations.

摘要

具有柔韧性和开放金属位点的材料对于无数应用至关重要。在本文中，我们报告了一种由 CuII 离子和柔性 -carborane 基连接体 [Cu(L1)(Solv)]•xSolv（1-DMA、1-DMF 和 1-MeOH；L1：1,7-二（4-羧基苯基）-1,7-二碳硼烷）组装的二维配位聚合物 (CP)。1-DMF 在溶剂处理（即 MeOH 和 CHCl）时经历了一个不寻常的可逆相转变的例子。溶剂交换，随后热激活提供了一种新的多孔相，其估计 Brunauer-Emmett-Teller（BET）表面积为 301 m g，并能够吸收 41 cm g 的 CO。该转化是可逆的，并且在多孔相中加入 DMF 时可以重新形成 1-DMF。我们提供的证据表明，可逆过程是由弱但有吸引力的 B-H∙∙∙Cu 相互作用的形成/断裂引起的，这是通过单晶 (SCXRD)、粉末 (PXRD) X 射线衍射、拉曼光谱和 DFT 计算的组合得出的。