Synthesis of anionic alkaline earth metal methanesulfonates bearing photo-responsive methylviologen†

IF 3.3 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR Dalton Transactions Pub Date : 2024-09-20 DOI:10.1039/D4DT02229G

Aishwarya Chauhan, Priyanka Chauhan and Ravi Shankar

{"title":"Synthesis of anionic alkaline earth metal methanesulfonates bearing photo-responsive methylviologen†","authors":"Aishwarya Chauhan, Priyanka Chauhan and Ravi Shankar","doi":"10.1039/D4DT02229G","DOIUrl":null,"url":null,"abstract":"Anionic coordination frameworks stabilized by methylviologen (MV2+; 1,1′-dimethyl 4,4′-bipyridinium) as a photochromic module are a distinct class of functional materials. Herein, we report the first examples of alkaline earth metal methanesulfonates [MV{Mg(OSO2Me)3(H2O)2}2] (1), [MV{Ca(OSO2Me)3(H2O)2}2] (2), [2{Mg(OSO2Me)2(H2O)4}MV·2OSO2Me] (3), and [Me4-pip{Ca2(OSO2Me)6(H2O)2}]n (4) incorporating methylviologen or tetra-N-methylpiperazinium (Me4-pip) as a charge-balancing cation. X-ray crystallographic studies of 1–3 emphasize the role of isolated ion-pairs for the construction of hydrogen-bonded supramolecular assemblies and the ability of methanesulfonates to donate electrons (centroid⋯O = 3.09–3.15 Å) to promote photoinduced one-electron reduction of MV2+ to an MV˙+ radical cation in the solid state. The inorganic framework in 4 adopts a layered motif with an inter-lamellar spacing of 11.8 Å, providing spatial expanse to accommodate the organic cations.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 41","pages":" 17014-17020"},"PeriodicalIF":3.3000,"publicationDate":"2024-09-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2024/dt/d4dt02229g","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}

引用次数: 0

Abstract

Anionic coordination frameworks stabilized by methylviologen (MV²⁺; 1,1′-dimethyl 4,4′-bipyridinium) as a photochromic module are a distinct class of functional materials. Herein, we report the first examples of alkaline earth metal methanesulfonates [MV{Mg(OSO₂Me)₃(H₂O)₂}₂] (1), [MV{Ca(OSO₂Me)₃(H₂O)₂}₂] (2), [2{Mg(OSO₂Me)₂(H₂O)₄}MV·2OSO₂Me] (3), and [Me₄-pip{Ca₂(OSO₂Me)₆(H₂O)₂}]_n (4) incorporating methylviologen or tetra-N-methylpiperazinium (Me₄-pip) as a charge-balancing cation. X-ray crystallographic studies of 1–3 emphasize the role of isolated ion-pairs for the construction of hydrogen-bonded supramolecular assemblies and the ability of methanesulfonates to donate electrons (centroid⋯O = 3.09–3.15 Å) to promote photoinduced one-electron reduction of MV²⁺ to an MV˙⁺ radical cation in the solid state. The inorganic framework in 4 adopts a layered motif with an inter-lamellar spacing of 11.8 Å, providing spatial expanse to accommodate the organic cations.

Abstract Image

查看原文

微信好友朋友圈 QQ好友复制链接

本刊更多论文

阴离子碱土金属-甲烷磺酸盐与光响应性甲基viologen 的结合方法

作为光致变色模块的阴离子配位框架由甲基维奥根（MV；1,1'-二甲基 4,4'-联吡啶鎓）稳定，属于一类独特的功能材料。在此，我们报告了碱土金属-甲磺酸盐的第一个实例：[MV{Mg(OSO2Me)3(H2O)2}2](1)、[MV{Ca(OSO2Me)3(H2O)2}2](2)、2{Mg（OSO2Me）2（H2O）4}MV-2OSO2Me](3) 和 [Me4-pip{Ca2(OSO2Me)6(H2O)2}]n(4) 以甲基维罗庚或四-N-甲基哌嗪（Me4-pip）作为电荷平衡阳离子。对 1-3 的 X 射线晶体学研究强调了孤立离子对在构建氢键超分子组装体中的作用，以及甲磺酸盐作为电子供体（centroid--O = 3.09-3.15Å）在固态中促进光诱导一电子将 MV 还原成 MV-+ 自由基阳离子的能力。4 中的无机框架采用了层间距为 11.8 Å 的分层结构，为容纳有机阳离子提供了广阔的空间。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文去求助

来源期刊

Dalton Transactions 化学-无机化学与核化学

CiteScore

6.60

自引率

7.50%

发文量

1832

审稿时长

1.5 months

期刊介绍： Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.