Star-shaped tetranuclear and dinuclear Ru/Os complexes: Interplay of synthesis, optoelectronic properties, and energy transfer

IF 4.2 3区工程技术 Q2 CHEMISTRY, APPLIED

Dyes and Pigments Pub Date : 2025-09-17 DOI:10.1016/j.dyepig.2025.113254

Hong-Ju Yin, Xiujian Mao, Hao Wang, Zining Liu, Shiwen Yu, Xiang Shen, Weijun Dai, Shubiao Xia, Feixiang Cheng

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引用次数: 0

Abstract

Photon-initiated energy transfer dynamics was studied in two tetranuclear complexes, Ru(RuL)₃ and Ru(LRu)₃, and three dinuclear complexes, RuLRu, RuLOs, and OsLRu, assembling ruthenium or osmium ion centers by bridging ligand L {Ru and Os represent [Ru(bpy)₂]²⁺and [Os(bpy)₂]²⁺ portions, respectively, where by = 2,2-bipyridyl; L = 2-(4′-methyl-2,2′-bipyridin-4-yl)-1H-imidazo[4,5-f]-1,10-phenanthroline}. In the tetranuclear complexes, the four metallic components are linked by bridging ligand L connecting the ruthenium atom and the moiety [Ru(bpy)₂]²⁺. The dinuclear and tetranuclear complexes show intense absorption throughout the UV–Vis region and display long-lived emission in the near-infrared region (NIR). The electrochemical studies reveal rich redox properties of the metal complexes, characterized by multiple reversible metal-based oxidation and ligand-centered reduction pairs. The excited state deactivation behavior of Ru(II) center demonstrates effective light-driven energy transfer in the heterodinuclear complexes, thereby generating osmium(II) NIR luminescence, which may be useful for the further development of NIR emission bioimagers. Emission and lifetime measurements reveal the efficient intramolecular energy transfer in homodinuclear and homotetranuclear complexes from Ru(II) ion center coordinated with L_phen to Ru(II) ion center coordinated with L_bpy. Interestingly, the homotetranuclear complexes emit intense luminescence. These multinuclear complexes efficiently absorb visible light by directing it from multiple chromophores to the subunit with the lowest excited in the excited state.

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星形四核和双核Ru/Os配合物：合成、光电性质和能量转移的相互作用

研究了两个四核配合物Ru(RuL)3和Ru(LRu)3以及三个双核配合物RuLRu、RuLOs和OsLRu通过桥接配体L (Ru和Os分别代表[Ru（bpy)2]2+和[Os(bpy)2]2+部分）组装钌或锇离子中心的光子引发的能量转移动力学，其中by = 2,2-联吡啶；L = 2 - (4 ' -methyl-2 2 ' -bipyridin-4-yl) 1 h-imidazo(4、5 f) 1, 10-phenanthroline}。在四核配合物中，四种金属组分通过桥接配体L连接钌原子和部分[Ru(bpy)2]2+。双核和四核配合物在整个紫外-可见区显示出强烈的吸收，并在近红外区显示出长寿命的发射。电化学研究表明，金属配合物具有丰富的氧化还原性质，具有多个可逆的金属基氧化和以配体为中心的还原对。钌（II）中心的激发态失活行为在异双核配合物中显示出有效的光驱动能量转移，从而产生锇（II）近红外发光，这可能对进一步开发近红外发射生物成像仪有用。发射和寿命测量揭示了同双核和同四核配合物中从与Lphen配位的Ru（II）离子中心到与Lbpy配位的Ru（II）离子中心的有效分子内能量转移。有趣的是，同型四核配合物发出强烈的发光。这些多核配合物通过将可见光从多个发色团引导到激发态中激发最低的亚基来有效地吸收可见光。

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来源期刊

Dyes and Pigments 工程技术-材料科学：纺织

CiteScore

8.20

自引率

13.30%

发文量

933

审稿时长

33 days

期刊介绍： Dyes and Pigments covers the scientific and technical aspects of the chemistry and physics of dyes, pigments and their intermediates. Emphasis is placed on the properties of the colouring matters themselves rather than on their applications or the system in which they may be applied. Thus the journal accepts research and review papers on the synthesis of dyes, pigments and intermediates, their physical or chemical properties, e.g. spectroscopic, surface, solution or solid state characteristics, the physical aspects of their preparation, e.g. precipitation, nucleation and growth, crystal formation, liquid crystalline characteristics, their photochemical, ecological or biological properties and the relationship between colour and chemical constitution. However, papers are considered which deal with the more fundamental aspects of colourant application and of the interactions of colourants with substrates or media. The journal will interest a wide variety of workers in a range of disciplines whose work involves dyes, pigments and their intermediates, and provides a platform for investigators with common interests but diverse fields of activity such as cosmetics, reprographics, dye and pigment synthesis, medical research, polymers, etc.