Kryczka Anna, Palion-Gazda Joanna, Choroba Katarzyna, Machura Barbara
Institute of Chemistry, University of Silesia, 9 Szkolna Str., 40-006 Katowice, Poland.
Molecules. 2025 May 29;30(11):2386. doi: 10.3390/molecules30112386.
Over the last nine decades, 2,2':6',2″-terpyridine (terpy) derivatives and their transition d-metal complexes have been extensively explored due to their unique and widely tuned optical, electrochemical, and biological properties. Terpyridyl transition metal complexes occupy a prominent position among functional molecular materials for applications in optoelectronics, life science, catalysis, and photocatalysis, as well as they have played a key role in determining structure-property relationships. This review summarizes the developments of amine-functionalized R-CH-terpy systems and their d-metal complexes, largely concentrating on their photophysical and electrochemical properties. Functionalization of the terpy core with the electron-rich group, attached to the central pyridine ring of the terpy backbone via the phenylene linker, gives rise to organic push-pull systems showing the photoinduced charge flow process from the peripheral donor substituent to the terpy acceptor. The introduction of amine-functionalized R-CH-terpy systems into the coordination sphere of a d-metal ion offers an additional way for controlling the photophysics of these systems, in agreement with the formation of the excited state of intraligand charge transfer (ILCT) nature. Within this review, a detailed discussion has been presented for R-CH-terpys modified with acyclic and cyclic amine groups and their Cr(III), Mn(I), Re(I), Fe(II), Ru(II), Os(II), Pt(II), and Zn(II) coordination compounds.
在过去的九十年里，2,2':6',2″-三联吡啶（terpy）衍生物及其过渡金属配合物因其独特且可广泛调节的光学、电化学和生物学性质而受到广泛研究。三联吡啶基过渡金属配合物在用于光电子学、生命科学、催化和光催化等领域的功能分子材料中占据显著地位，并且在确定结构-性质关系方面发挥了关键作用。本综述总结了胺官能化的R-CH-terpy体系及其d金属配合物的发展情况，主要集中在它们的光物理和电化学性质上。通过亚苯基连接基连接到terpy主链的中心吡啶环上的富电子基团对terpy核心进行官能化，产生了有机推拉体系，显示出从外围供体取代基到terpy受体的光诱导电荷流动过程。将胺官能化的R-CH-terpy体系引入d金属离子的配位球中，为控制这些体系的光物理性质提供了另一种方法，这与形成配体内电荷转移（ILCT）性质的激发态相一致。在本综述中，对用无环和环状胺基团修饰的R-CH-terpys及其Cr(III)、Mn(I)、Re(I)、Fe(II)、Ru(II)、Os(II)、Pt(II)和Zn(II)配位化合物进行了详细讨论。
