Le Garrec Stéphen, Martins-Bessa David, Wolff Mariusz, Delavaux-Nicot Béatrice, Mallet-Ladeira Sonia, Serpentini Charles-Louis, Benoist Eric, Bedos-Belval Florence, Fery-Forgues Suzanne
SPCMIB, CNRS UMR 5068, Université de Toulouse III Paul Sabatier, 118 route de Narbonne, 31062 Toulouse cedex 9, France.
Institut für Funktionelle Materialien und Katalyse, Universität Wien, Währinger Straße 38-42, 1090 Wien, Austria.
Dalton Trans. 2024 Oct 15;53(40):16512-16529. doi: 10.1039/d4dt01907e.
Dinuclear Re(I) complexes have proportionally been much less studied than mononuclear analogues. In particular, very little information is available about their solid-state emission properties. In this work, two structural isomers of dinuclear complexes (Bi-Re-metaPhe and Bi-Re-paraPhe), which differ by the relative position of the coordination spheres on a central phenyl ring, were synthesized and compared with each other and with the parent mononuclear compound (Mono-Re-Phe), from a theoretical and experimental point of view. In solution, the electronic, electrochemical and spectroscopic properties of the dinuclear complexes were almost identical, and rather close to those of the monomer. In the solid state, the photoluminescence (PL) efficiency of dimers was not higher than that of the monomer, but a clear mechanoresponsive luminescence (MRL) effect appeared only for the former ones. The positional isomerism influenced the amplitude of this effect, as well as the aggregation-induced emission (AIE) properties in a water-acetonitrile mixture. This study reveals the importance of positional isomerism to modulate the emission properties in the solid state. It also shows the advantage of dinuclear structures to access new MRL-active materials.
双核铼（I）配合物的研究程度相比单核类似物要少得多。特别是，关于它们的固态发光性质的信息非常少。在这项工作中，从理论和实验的角度合成了双核配合物的两种结构异构体（Bi-Re-间苯丙氨酸和Bi-Re-对苯丙氨酸），它们在中心苯环上配位球的相对位置不同，并将它们相互比较，还与母体单核化合物（Mono-Re-苯丙氨酸）进行了比较。在溶液中，双核配合物的电子、电化学和光谱性质几乎相同，并且与单体的性质相当接近。在固态下，二聚体的光致发光（PL）效率不高于单体，但仅前者出现了明显的机械响应发光（MRL）效应。位置异构影响了这种效应的幅度，以及在水-乙腈混合物中的聚集诱导发光（AIE）性质。这项研究揭示了位置异构对调节固态发光性质的重要性。它还展示了双核结构在获得新型MRL活性材料方面的优势。
