A new family of Pt(II) isocyanide complexes with NNC-type pincer ligands: Correlation between structural features and aggregation-induced emission

IF 4.2 3区材料科学 Q2 MATERIALS SCIENCE, MULTIDISCIPLINARY Optical Materials Pub Date : 2025-03-11 DOI:10.1016/j.optmat.2025.116926

Elizaveta V. Durova, Ekaterina E. Galenko, Andrey A. Shtyrov, Mikhail N. Ryazantsev, Kristina S. Kisel, Julia R. Shakirova, Sergey P. Tunik

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Abstract

Four square-planar [(NNC)Pt(CN-Xyl)]OTf complexes bearing a novel tridentate ligands (NNC-1/4) were synthesized and fully characterized. Photophysical properties of the obtained compounds were investigated in acetonitrile solution, solid state and aqueous dispersion. It was shown that the complexes in their monomeric form exhibit moderate phosphorescence in the visible and NIR regions with a clear correlation of emission maxima with the nature of the cyclometalated fragment in the pincer ligand. Complexes with substituted phenyl ring as the C-coordinated fragment (NNC-1/3)Pt(CN-Xyl) demonstrate aggregation induced emission (AIE) with a strong red shift of emission bands in the solid state and water dispersions, the magnitude of which correlates with the packing mode of the molecules, i.e., with the number of platinum metal centers taking part in formation of aggregates. The complex containing benzothienyl C-coordinated moiety (NNC-4)Pt(CN-Xyl) shows no AIE effects that is in agreement with its structural features, which do not allow formation of the aggregates with short Pt–Pt contacts. All correlations between the photophysical behavior of the complexes, their composition and structural parameters were also confirmed by quantum-chemical calculations based on the analysis of the model systems containing monomers, dimers and trimers of the starting complexes.

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一类新的具有nnc型钳形配体的铂（II）异氰化物配合物：结构特征与聚集诱导发射的相关性

合成了四个带有新型三齿配体（NNC-1/4）的方形平面[(NNC)Pt(CN-Xyl)]OTf配合物，并对其进行了表征。研究了所得化合物在乙腈溶液、固体和水分散体中的光物理性质。结果表明，单体形式的配合物在可见光和近红外区表现出适度的磷光，其最大发光值与钳形配体中环金属化片段的性质有明显的相关性。以取代苯环为c配位片段的配合物（NNC-1/3）Pt（CN-Xyl）表现出聚集诱导发射（AIE），在固态和水分散体中发射带发生了强烈的红移，其大小与分子的堆积方式有关，即与参与聚集形成的铂金属中心的数量有关。含有苯并噻吩基c -配位部分（NNC-4）Pt（CN-Xyl）的配合物没有AIE效应，这与其结构特征一致，不允许形成具有短Pt - Pt接触的聚集体。通过对初始配合物的单体、二聚体和三聚体模型体系的分析，量子化学计算证实了配合物的光物理行为、组成和结构参数之间的所有相关性。

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来源期刊

Optical Materials 工程技术-材料科学：综合

CiteScore

6.60

自引率

12.80%

发文量

1265

审稿时长

38 days

期刊介绍： Optical Materials has an open access mirror journal Optical Materials: X, sharing the same aims and scope, editorial team, submission system and rigorous peer review. The purpose of Optical Materials is to provide a means of communication and technology transfer between researchers who are interested in materials for potential device applications. The journal publishes original papers and review articles on the design, synthesis, characterisation and applications of optical materials. OPTICAL MATERIALS focuses on: • Optical Properties of Material Systems; • The Materials Aspects of Optical Phenomena; • The Materials Aspects of Devices and Applications. Authors can submit separate research elements describing their data to Data in Brief and methods to Methods X.