Palion-Gazda Joanna, Kwiecień Aleksandra, Choroba Katarzyna, Penkala Mateusz, Erfurt Karol, Machura Barbara
Institute of Chemistry, University of Silesia, Szkolna 9, 40-006 Katowice, Poland.
Department of Chemical Organic Technology and Petrochemistry, Silesian University of Technology, Krzywoustego 4, 44-100 Gliwice, Poland.
Inorg Chem. 2025 Jan 13;64(1):646-661. doi: 10.1021/acs.inorgchem.4c03769. Epub 2024 Dec 26.
This paper provides extensive studies of [IrCl(Ph-py)(morph-CH-terpy-κN)]PF (), [Ir(Ph-py)(morph-CH-terpy-κN)]PF (), [IrCl(Ph-py)(Ph-terpy-κN)]PF (), and [Ir(Ph-py)(Ph-terpy-κN)]PF () designed to demonstrate the possibility of controlling the photophysical properties of mono- and bis-cyclometalated complexes [IrCl(Ph-py)(R-CH-terpy-κN)]PF and [Ir(Ph-py)(R-CH-terpy-κN)]PF through a remote electron-donating substituent introduced into the 4'-position of 2,2':6',2″-terpyridine (terpy) via the phenyl linker. The attachment of the morpholinyl (morph) group was evidenced to induce dramatic changes in the emission characteristics of the monocyclometalated Ir(III) systems with coordinated R-CH-terpy ligand (κN). In solution, the obtained complex [IrCl(Ph-py)(morph-CH-terpy-κN)]PF was found to be a rare example of dual-emissive Ir(III) systems. Within the series [Ir(Ph-py)(R-CH-terpy-κN)]PF bearing the R-CH-terpy ligand bound to the central ion in a bidentate coordination mode, the appended electron-donating morpholinyl group induced a minor effect on the emission maximum, but it was found to be an effective tool for extending the excited-state lifetime, further prolonging with the increase of solvent polarity. The results of this work are of high significance for better understanding the push-pull effect and dual-emission phenomena in Ir-based luminophores, as well as developing chromophores with prolonged emission lifetimes.
本文对[IrCl(Ph-py)(morph-CH-terpy-κN)]PF（）、[Ir(Ph-py)(morph-CH-terpy-κN)]PF（）、[IrCl(Ph-py)(Ph-terpy-κN)]PF（）和[Ir(Ph-py)(Ph-terpy-κN)]PF（）进行了广泛研究，旨在证明通过经由苯基连接基引入到2,2':6',2″-三联吡啶（terpy）的4'-位的远程供电子取代基来控制单环和双环金属化配合物[IrCl(Ph-py)(R-CH-terpy-κN)]PF和[Ir(Ph-py)(R-CH-terpy-κN)]PF的光物理性质的可能性。已证明吗啉基（morph）基团的连接会引起具有配位R-CH-terpy配体（κN）的单环金属化Ir(III)体系发射特性的显著变化。在溶液中，所得到的配合物[IrCl(Ph-py)(morph-CH-terpy-κN)]PF被发现是双发射Ir(III)体系的一个罕见例子。在以双齿配位模式将R-CH-terpy配体与中心离子结合的[Ir(Ph-py)(R-CH-terpy-κN)]PF系列中，所连接的供电子吗啉基对发射最大值产生较小影响，但它被发现是延长激发态寿命的有效工具，随着溶剂极性的增加进一步延长。这项工作的结果对于更好地理解基于Ir的发光体中的推挽效应和双发射现象以及开发具有延长发射寿命的发色团具有重要意义。
