Playing with Polyoxometalates to Build Molecular Materials Exhibiting Negative Solid-State Photochromism

IF 4.7 2区化学 Q1 CHEMISTRY, INORGANIC & NUCLEAR

Inorganic Chemistry Pub Date : 2025-09-22 DOI:10.1021/acs.inorgchem.5c02938

Cédric Viravaux, Mohamed Haouas, Anne Dolbecq, Jérôme Marrot, Pierre Mialane, Rémi Dessapt, Olivier Oms

{"title":"Playing with Polyoxometalates to Build Molecular Materials Exhibiting Negative Solid-State Photochromism","authors":"Cédric Viravaux, Mohamed Haouas, Anne Dolbecq, Jérôme Marrot, Pierre Mialane, Rémi Dessapt, Olivier Oms","doi":"10.1021/acs.inorgchem.5c02938","DOIUrl":null,"url":null,"abstract":"Four novel ionic assemblies combining polyoxometalates (POMs) and the cationic photochromic spiropyran SPPy+ (1′,3′,3′-trimethyl-6-nitro-8-pyridiniomethylspiro[2H-[1]benzopyran-2,2′-indoline]), namely, (SPPy)2[W6O19]·2CH3CN, (SPPy)2.6(H)0.4[PW12O40]·CH3CN, (SPPy)2.1(H)1.9[β-Mo8O26]·CH3CN, and (SPPy)3.7(H)0.3[β-Mo8O26], were synthesized and extensively characterized using complementary techniques, including structural characterization of (SPPy)2[W6O19]·2CH3CN by X-ray diffraction. In particular, solid-state 13C NMR spectroscopy was used for the first time on POM/Spiro compounds to assess the proportion of the merocyanine form in these supramolecular materials. Strikingly, in contrast to the deeply colored (SPPy)2.6(H)0.4[PW12O40]·CH3CN and (SPPy)2.1(H)1.9[β-Mo8O26]·CH3CN assemblies, which are nonphotochromic in the solid state at room temperature, (SPPy)2[W6O19]·2CH3CN and (SPPy)3.7(H)0.3[β-Mo8O26] exhibit strong photocontrast under soft-light irradiation. These observations highlight the crucial role of both the nature of the POM and the synthesis conditions on the optical properties of the final materials. The solid-state photochromic properties of these species have been fully investigated, and the coloration and fading kinetic parameters have been determined. Importantly, once discolored, (SPPy)2[W6O19]·2CH3CN and (SPPy)3.7(H)0.3[β-Mo8O26] turn back to a colored state in the dark, making them the first POM/Spiro hybrid materials to exhibit solid-state negative photochromism.","PeriodicalId":40,"journal":{"name":"Inorganic Chemistry","volume":"31 1","pages":""},"PeriodicalIF":4.7000,"publicationDate":"2025-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Inorganic Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/acs.inorgchem.5c02938","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}

引用次数: 0

Abstract

Four novel ionic assemblies combining polyoxometalates (POMs) and the cationic photochromic spiropyran SPPy⁺ (1′,3′,3′-trimethyl-6-nitro-8-pyridiniomethylspiro[2H-[1]benzopyran-2,2′-indoline]), namely, (SPPy)₂[W₆O₁₉]·2CH₃CN, (SPPy)_2.6(H)_0.4[PW₁₂O₄₀]·CH₃CN, (SPPy)_2.1(H)_1.9[β-Mo₈O₂₆]·CH₃CN, and (SPPy)_3.7(H)_0.3[β-Mo₈O₂₆], were synthesized and extensively characterized using complementary techniques, including structural characterization of (SPPy)₂[W₆O₁₉]·2CH₃CN by X-ray diffraction. In particular, solid-state ¹³C NMR spectroscopy was used for the first time on POM/Spiro compounds to assess the proportion of the merocyanine form in these supramolecular materials. Strikingly, in contrast to the deeply colored (SPPy)_2.6(H)_0.4[PW₁₂O₄₀]·CH₃CN and (SPPy)_2.1(H)_1.9[β-Mo₈O₂₆]·CH₃CN assemblies, which are nonphotochromic in the solid state at room temperature, (SPPy)₂[W₆O₁₉]·2CH₃CN and (SPPy)_3.7(H)_0.3[β-Mo₈O₂₆] exhibit strong photocontrast under soft-light irradiation. These observations highlight the crucial role of both the nature of the POM and the synthesis conditions on the optical properties of the final materials. The solid-state photochromic properties of these species have been fully investigated, and the coloration and fading kinetic parameters have been determined. Importantly, once discolored, (SPPy)₂[W₆O₁₉]·2CH₃CN and (SPPy)_3.7(H)_0.3[β-Mo₈O₂₆] turn back to a colored state in the dark, making them the first POM/Spiro hybrid materials to exhibit solid-state negative photochromism.

Abstract Image

查看原文本刊更多论文

用多金属氧酸盐制备负固态光致变色分子材料

合成了四种新型离子组合，即（SPPy）2[W6O19]·2CH3CN、（SPPy）2.6(H)0.4[PW12O40]·CH3CN、（SPPy）2.1(H)1.9[β-Mo8O26]·CH3CN和（SPPy）3.7(H)0.3[β-Mo8O26]·2CH3CN，并利用互补技术对（SPPy）2[W6O19]·2CH3CN进行了广泛的表征，包括x射线衍射表征（SPPy）2[W6O19]·2CH3CN的结构。特别是，固态13C核磁共振光谱首次用于POM/Spiro化合物，以评估这些超分子材料中merocyanine形式的比例。引人注目的是，与深彩色（SPPy）2.6(H)0.4[PW12O40]·CH3CN和（SPPy）2.1(H)1.9[β-Mo8O26]·CH3CN在室温下的固态非光致变色相比，（SPPy）2[W6O19]·2CH3CN和（SPPy）3.7(H)0.3[β-Mo8O26]在柔和光照射下表现出强烈的光致变色。这些观察结果突出了POM的性质和合成条件对最终材料光学性质的关键作用。研究了这些物质的固态光致变色性能，确定了其显色和褪色动力学参数。重要的是，一旦变色，（SPPy）2[W6O19]·2CH3CN和（SPPy）3.7(H)0.3[β-Mo8O26]在黑暗中会恢复到彩色状态，使它们成为第一个表现出固态负光致变色的POM/Spiro杂化材料。

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分钟内获得全文求助全文

来源期刊

Inorganic Chemistry 化学-无机化学与核化学

CiteScore

7.60

自引率

13.00%

发文量

1960

审稿时长

1.9 months

期刊介绍： Inorganic Chemistry publishes fundamental studies in all phases of inorganic chemistry. Coverage includes experimental and theoretical reports on quantitative studies of structure and thermodynamics, kinetics, mechanisms of inorganic reactions, bioinorganic chemistry, and relevant aspects of organometallic chemistry, solid-state phenomena, and chemical bonding theory. Emphasis is placed on the synthesis, structure, thermodynamics, reactivity, spectroscopy, and bonding properties of significant new and known compounds.