中国科学院理化技术研究所陈勇团队报道了具有旋转自由度的双配位金（I）配合物——一个集成热激活延迟荧光、多态性和线性偏振发光的平台。相关研究成果发表在2024年9月11日出版的《德国应用化学》。

双配位新型金属配合物已被用于各种应用。

该文合成了一种新的供体-金属-受体（D-M-A）配合物PZI-Au-TOT，该配合物使用大体积吡嗪稠合的N-杂环卡宾（PZI）和三氧基三苯胺（TOT）配体。PZI-Au-TOT在掺杂薄膜中显示出良好的热激活延迟荧光（TADF），量子产率为93%。PZI-Au-TOT晶体同时表现出TADF、多态性和线性偏振发光（LPL）。

在560至655 nm范围内具有广泛变化峰的多晶型依赖发射特性，归因于分离单体、离散π-π堆叠二聚体或二聚体PLUS的不同堆积模式。PZI-Au-TOT的两个定义明确的微晶表现出线性偏振的热激活延迟荧光，偏振度高达0.64。

该项工作表明，D-M-A型配合物的分子旋转灵活性通过操纵超分子聚集，将多种功能整合到一个配合物中。这种复合物有望成为制造先进光子应用晶体材料的多功能平台。

附：英文原文

Title: Two-Coordinate Gold(I) Complex with Rotational Freedom: A Platform Integrating Thermally Activated Delayed Fluorescence, Polymorphism, and Linearly Polarized Luminescence

Author: Xi Zhang, Xiu-Fang Song, Shan Jiang, Yi-Ge Yao, Xiaoyong Chang, Yunan Gao, Kai Li, Yong Chen

Issue&Volume: 2024-09-11

Abstract: Two-coordinate coinage metal complexes have been exploited for various applications. Herein, a new donor-metal-acceptor (D-M-A) complex PZI-Au-TOT, using bulky pyrazine-fused N-heterocyclic carbene (PZI) and trioxytriphenylamine (TOT) ligands, was synthesized. PZI-Au-TOT displays decent thermally activated delayed fluorescence (TADF) with a quantum yield of 93% in doped film. The crystals of PZI-Au-TOT show simultaneous TADF, polymorphism, and linearly polarized luminescence (LPL). The polymorph-dependent emission properties with widely varied peaks from 560 to 655 nm are attributed to different packing modes in terms of isolated monomers, discrete π-π stacked dimers or dimer PLUS. Two well-defined microcrystals of PZI-Au-TOT exhibit linearly polarized thermally activated delayed fluorescence with a degree of polarization up to 0.64. This work demonstrates that the molecular rotational flexibility of D-M-A type complexes endows an integration of multiple functions into one complex through manipulation of supramolecular aggregation. This type of complexes is expected to serve as a versatile platform for the fabrication of crystal materialsfor advanced photonic applications.

DOI: 10.1002/anie.202414892

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202414892