Xu Fei, Liu Ai-Ju, Han Song-De, Pan Jie, Wang Guo-Ming
College of Chemistry and Chemical Engineering, Qingdao University, Shandong, 266071, P. R. China.
Chemistry. 2021 Mar 8;27(14):4709-4714. doi: 10.1002/chem.202005402. Epub 2021 Feb 9.
As a significant class of photochromic materials, crystalline hybrid photochromic materials (CHPMs) have attracted widespread attention of researchers because of their possibilities for generating other photoresponsive properties and advantages in understanding the underlying relationship between structure and photoresponsive performance. The predesign of suitable ligands plays a major role in generating desirable CHPMs. Hitherto, most CHPMs have been built from photodeformable or photoresponsive tectons. However, the synthesis of these ligands is usually time-consuming and expensive, and this greatly restricts their large-scale preparation and practical application. Therefore, it is necessary to explore new families of CHPMs besides the existing CHPMs. Herein, a simple and general method for constructing CHPMs by decorating metal nitrate with a coplanar bipyridine moiety, namely 1,10-phenanthroline (phen), is reported. The resulting products exhibit photocoloration in response to Xe-lamp irradiation. The electron transfer (ET) from the coplanar NO species (as π-electron donors, π-EDs) to coplanar phen moieties (as π-electron acceptors, π-EAs) is responsible for the resulting photochromism. The influence of the coordination environment and central metal ion on the photochromism was also studied. This work demonstrates that the introduction of coplanar organic tectons as π-EAs to metal nitrates as π-EDs with the collaboration of ET and coordination-assembly strategies is a simple and general method to manufacture CHPMs.
作为一类重要的光致变色材料,晶体混合光致变色材料(CHPMs)因其具有产生其他光响应特性的可能性以及在理解结构与光响应性能之间潜在关系方面的优势,而吸引了研究人员的广泛关注。合适配体的预设计在生成理想的CHPMs中起着主要作用。迄今为止,大多数CHPMs是由光可变形或光响应性结构单元构建而成。然而,这些配体的合成通常既耗时又昂贵,这极大地限制了它们的大规模制备和实际应用。因此,除了现有的CHPMs之外,有必要探索新的CHPMs家族。在此,报道了一种通过用共面联吡啶部分(即1,10 - 菲咯啉(phen))修饰金属硝酸盐来构建CHPMs的简单通用方法。所得产物在氙灯照射下呈现光致变色。从共面的NO物种(作为π电子供体,π - EDs)到共面的phen部分(作为π电子受体,π - EAs)的电子转移(ET)导致了光致变色现象。还研究了配位环境和中心金属离子对光致变色的影响。这项工作表明,通过电子转移和配位组装策略的协同作用,将共面有机结构单元作为π - EAs引入到作为π - EDs的金属硝酸盐中,是一种制备CHPMs的简单通用方法。