Aishwarya Chauhan, Priyanka Chauhan and Ravi Shankar
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Herein, we report the first examples of alkaline earth metal methanesulfonates [MV{Mg(OSO<small><sub>2</sub></small>Me)<small><sub>3</sub></small>(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>}<small><sub>2</sub></small>] (<strong>1</strong>), [MV{Ca(OSO<small><sub>2</sub></small>Me)<small><sub>3</sub></small>(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>}<small><sub>2</sub></small>] (<strong>2</strong>), [2{Mg(OSO<small><sub>2</sub></small>Me)<small><sub>2</sub></small>(H<small><sub>2</sub></small>O)<small><sub>4</sub></small>}MV·2OSO<small><sub>2</sub></small>Me] (<strong>3</strong>), and [Me<small><sub>4</sub></small>-pip{Ca<small><sub>2</sub></small>(OSO<small><sub>2</sub></small>Me)<small><sub>6</sub></small>(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>}]<small><sub><em>n</em></sub></small> (<strong>4</strong>) incorporating methylviologen or tetra-<em>N</em>-methylpiperazinium (Me<small><sub>4</sub></small>-pip) as a charge-balancing cation. X-ray crystallographic studies of <strong>1–3</strong> 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 MV<small><sup>2+</sup></small> to an MV˙<small><sup>+</sup></small> radical cation in the solid state. The inorganic framework in <strong>4</strong> adopts a layered motif with an inter-lamellar spacing of 11.8 Å, providing spatial expanse to accommodate the organic cations.</p>","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":"{\"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\":\"<p >Anionic coordination frameworks stabilized by methylviologen (MV<small><sup>2+</sup></small>; 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(OSO<small><sub>2</sub></small>Me)<small><sub>3</sub></small>(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>}<small><sub>2</sub></small>] (<strong>1</strong>), [MV{Ca(OSO<small><sub>2</sub></small>Me)<small><sub>3</sub></small>(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>}<small><sub>2</sub></small>] (<strong>2</strong>), [2{Mg(OSO<small><sub>2</sub></small>Me)<small><sub>2</sub></small>(H<small><sub>2</sub></small>O)<small><sub>4</sub></small>}MV·2OSO<small><sub>2</sub></small>Me] (<strong>3</strong>), and [Me<small><sub>4</sub></small>-pip{Ca<small><sub>2</sub></small>(OSO<small><sub>2</sub></small>Me)<small><sub>6</sub></small>(H<small><sub>2</sub></small>O)<small><sub>2</sub></small>}]<small><sub><em>n</em></sub></small> (<strong>4</strong>) incorporating methylviologen or tetra-<em>N</em>-methylpiperazinium (Me<small><sub>4</sub></small>-pip) as a charge-balancing cation. 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引用次数: 0
摘要
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。
Synthesis of anionic alkaline earth metal methanesulfonates bearing photo-responsive methylviologen†
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.
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.
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