河南大学赵俊伟团队报道了刚柔配体修饰镧系硒钨酸盐及其光致发光特性。相关研究成果于2024年6月24日发表在国际顶尖学术期刊《结构化学》。

目前，有机-无机杂化镧系元素掺杂的多金属氧酸盐（POMs）已成为一个突出的研究领域。

该文采用一种简单的原料组装方法合成了两种新的混合有机配体修饰镧系元素（Ln）的硒钨酸盐[H₂N(CH₃)₂]₁₆Na₂ [Ln₄(H₂O)₆(HPZDA)₂(HFMA)₂W₈O₂₁][B-α-SeW₉O₃₃]₄·29H₂O (Ln = Sm³⁺ (1), La³⁺ (2); H₂PZDA = 2,3-吡嗪二羧酸, H₂FMA = 富马酸)。1和2与由四个三棘Keggin[B-α-SeW₉O₃₃]^8–（{SeW₉}）链段，和一个刚性-柔性配体修饰的十二碳原子核W–Ln杂金属[Ln₄(H₂O)₆(HPZDA)₂(HFMA)₂W₈O₂₁]¹⁴⁺簇构建的聚阴离子同构。

此外，1在室温下的固态荧光光谱主要表现出Sm³⁺阳离子的特征发射峰。此外，通过时间分辨光谱法证明了从{SeW_9}到1中Sm³⁺离子的能量转移。

该工作为构建新型聚甲醛衍生物和聚甲醛基荧光材料，提供了一种可行的双配体协同策略。

附：英文原文

Title: Rigid-flexible-ligand-ornamented lanthanide-incorporated selenotungstates and photoluminescence properties

Author:Tiantian Gong, Yanan Chen, Shuo Wang, Miao Wang, Junwei Zhao

Issue&Volume: 2024-06-24

Abstract: Currently, organic–inorganic hybrid lanthanide-incorporated polyoxometalates (POMs) have emerged as a prominent research area. Herein, we employed a simple raw material assembly method to synthesize two neoteric mixed-organic -ligand-ornamented lanthanide (Ln) incorporated selenotungstates [H2N(CH3)2]16Na2 [Ln4(H2O)6(HPZDA)2(HFMA)2W8O21][B-α-SeW9O33]4·29H2O (Ln = Sm3+ (1), La3+ (2); H2PZDA = 2,3-pyrazine dicarboxylic acid, H2FMA = fumaric acid). 1 and 2 are isomorphic with the polyanions constructed from four trivacant Keggin [B-α-SeW9O33]8– ({SeW9}) segments and a rigid-flexible-ligand-ornamented dodeca-nuclear W–Ln heterometallic [Ln4(H2O)6(HPZDA)2(HFMA)2W8O21]14+ cluster. Moreover, the solid-state fluorescence spectrum of 1 at room temperature mainly exhibits the characteristic emission peak of Sm3+ cations. Additionally, energy transfer from {SeW9} to Sm3+ ions in 1 has been demonstrated by time-resolved spectroscopy. This work presents a feasible dual-ligand synergistic strategy for constructing novel POM derivatives and POM-based fluorescent materials.

DOI: 10.1016/j.cjsc.2024.100370

Source: http://cjsc.ac.cn/cms/issues/653