Kang Run-Kun, Dong Ya-Yu, Cao Jia-Peng, Luo Xi-Ming, Du Ze-Yu, Zhu Dunru, Xu Yan
College of Chemical Engineering, State Key Laboratory of Materials-Oriented Chemical Engineering, Nanjing Tech University, Nanjing, 210009, P. R. China.
Chemistry. 2021 Jan 18;27(4):1301-1305. doi: 10.1002/chem.202004083. Epub 2020 Dec 15.
An unprecedented bird-nest high-nuclear molybdenum(V) cobalto-phosphate nanosized wheel modified by imidazole (im) and pyridine (py), {[H (Mo O )(Co O) Co (PO ) (py) (EtOH) (H O) ]- @[(Him) (Hpy)]}(N-Et-py)(H PO )(py) (EtOH)⋅12 H O (1), has been successfully synthesized by self-assembly. The anionic huge wheel consists of two rare {Co O} squares, four {Co } tetramers, four {Mo } tetramers and four {Mo } dimers, linked by bridging oxygen atoms and [PO ] groups and encloses two imidazolium cations and a protonated pyridium for charge balance. Surprisingly, 1 represents the first twisted wheel-shaped cluster with a record high-nuclear molybdenum(V) cobalto-phosphate. The delocalized electron effects of the cluster are enhanced with the help of coordinated py ligands, which endows 1 with an excellent third-order nonlinear optical (NLO) response. Additionally, 1 also shows a better photocatalytic water oxidation activity than Co(NO ) with the O production of 205 μmol during 6 h in the absence of the [Ru(bpy) ] photosensitizer.
一种前所未有的由咪唑（im）和吡啶（py）修饰的鸟巢状高核钼（V）钴磷酸盐纳米尺寸轮，{[H (Mo O )(Co O) Co (PO ) (py) (EtOH) (H O) ]- @[(Him) (Hpy)]}(N-Et-py)(H PO )(py) (EtOH)⋅12 H O (1)，已通过自组装成功合成。阴离子大轮由两个罕见的{Co O}正方形、四个{Co }四聚体、四个{Mo }四聚体和四个{Mo }二聚体组成，通过桥连氧原子和[PO ]基团相连，并包围两个咪唑阳离子和一个质子化吡啶以实现电荷平衡。令人惊讶的是，1代表了第一个具有创纪录高核钼（V）钴磷酸盐的扭曲轮状簇。簇的离域电子效应在配位py配体的帮助下得到增强，这赋予1优异的三阶非线性光学（NLO）响应。此外，在没有[Ru(bpy) ]光敏剂的情况下，1在6小时内的O 产量为205 μmol，其光催化水氧化活性也比Co(NO )更好。
