Water-soluble dinuclear iridium( iii ) and ruthenium( ii ) bis-terdentate complexes: photophysics and electrochemiluminescence
Water-soluble dinuclear iridium( iii ) and ruthenium( ii ) bis-terdentate complexes: photophysics and electrochemiluminescence
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水溶性双核铱( iii ) 和钌( ii ) 双齿配合物：光物理和电化学发光
DOI：
10.1039/d2dt02104h
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发表时间：
2022
影响因子：
4
通讯作者：
Sun, Wenfang
中科院分区：
文献类型：
--
作者：
Liu, Bingqing;Yang, Xin;Jabed, Mohammed;Kilina, Svetlana;Yang, Zhengchun;Sun, Wenfang
报道了4个以4′-苯基-2，2 ′：6′，2 ′′-三联吡啶（tpy）或1，3-二（吡啶-2-基）-4，6-二甲苯（N^C^N）为配体，以2，7-二（2，2 ′：6 ′，2 ′′-三联吡啶）芴为配体的水溶性双核Ir（III）和Ru（II）配合物（1-4）的合成、物理性质和电化学发光（ECL）。通过光谱方法（包括紫外-可见吸收、发射和瞬态吸收）和含时密度泛函理论（TDDFT）计算评估了tpy或N^C^N配体和金属中心对1-4的电子物理性质的影响。这些配合物表现出不同的单重态和三重态激发态的性质时，终端封端的三齿配体和金属中心的变化。在中性磷酸盐缓冲溶液（PBS）中，加入三丙胺（TPA）作为共反应物，研究了水溶性较好的配合物1-3的电致发光性能，其电致发光强度由大到小的顺序为3 > 1 > 2。含[Ru（tpy）2]2+单元的配合物3显示出更明显的电化学发光信号，使其类似物具有进一步电化学发光研究的潜力。
The synthesis, photophysics, and electrochemiluminescence (ECL) of four water-soluble dinuclear Ir(III) and Ru(II) complexes (1–4) terminally-capped by 4′-phenyl-2,2′:6′,2′′-terpyridine (tpy) or 1,3-di(pyrid-2-yl)-4,6-dimethylbenzene (N^C^N) ligands and linked by a 2,7-bis(2,2′:6′,2′′-terpyridyl)fluorene with oligoether chains on C9 are reported. The impact of the tpy or N^C^N ligands and metal centers on the photophysical properties of 1–4 was assessed by spectroscopic methods including UV-vis absorption, emission, and transient absorption, and by time-dependent density functional theory (TDDFT) calculations. These complexes exhibited distinct singlet and triplet excited-state properties upon variation of the terminal-capping terdentate ligands and the metal centers. The ECL properties of complexes 1–3 with better water solubility were investigated in neutral phosphate buffer solutions (PBS) by adding tripropylamine (TPA) as a co-reactant, and the observed ECL intensity followed the descending order of 3 > 1 > 2. Complex 3 bearing the [Ru(tpy)2]2+ units displayed more pronounced ECL signals, giving its analogues great potential for further ECL study.