Diruthenium(II)diacetylide organometallic complexes with thienylethynyl bridging units: Synthesis, characterization and electrochemical properties

IF 1.7 4区 化学 Q3 CHEMISTRY, MULTIDISCIPLINARY
Sourav Saha Roy, Supriya Das, Sanjib K Patra
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Abstract

A series of soluble diruthenium(II)diacetylide complexes (M1-M3) by varying thienlylethynyl bridging ligands have been achieved by treating the appropriate thienylethynyl spacers (B1, B2 and B3 with one, two and three units of thienylethynyl respectively) with [Ru(dppe)Cp*Cl] and KF in THF/MeOH medium. The synthesized diruthenium(II) organometallic complexes have been thoroughly characterized by multinuclear NMR spectroscopy, FTIR and mass spectrometry. The photophysical and electrochemical studies of these soluble wire-like Ru(II) organometallic complexes (M1-M3) with aromatic π-extended bridges have been carried out to comprehend the electronic and electrochemical properties. The electronic delocalization in Ru(II)–C≡C–Ar–C≡C–Ru(II) (Ar = aromatic bridging ligand) conjugate through the bridging backbone is dependent on the bridging spacers. Potential difference (ΔE1/2) and comproportionation constant (Kc) decrease with increasing the length of the thienylethynyl unit. The mixed-valence species, generated by single-electron oxidation, exhibits absorption in the near-infrared (NIR) region. Moreover, FTIR studies also reveal a change in \(\bar{\upsilon }\)(Ru-C≡C) stretching frequency of the mixed valence species, suggesting considerable participation of the bridging ligand in redox processes.

Graphical abstract

Electrochemical and electronic properties of the diruthenium(II)diacetylide organometallic conjugates have been modulated by varying the number of thienylethynyl bridging units.

Abstract Image

具有噻吩乙炔桥接单元的钌(II)二乙酰有机金属配合物:合成、表征和电化学特性
在THF/MeOH介质中,用[Ru(dppe)Cp*Cl]和KF处理合适的噻吩乙基间隔物(分别含1、2和3个噻吩乙基单位的B1、B2和B3),得到了一系列噻吩乙基桥接配体可溶的二乙基二乙酰配合物(M1-M3)。用多核核磁共振、红外光谱和质谱等手段对合成的金属有机配合物进行了表征。本文对这些具有芳香π扩展桥的可溶线状Ru(II)有机金属配合物(M1-M3)进行了光物理和电化学研究,以了解其电子和电化学性质。Ru(II) -C≡C-Ar-C≡C-Ru (II) (Ar =芳香桥接配体)通过桥接主链共轭的电子离域依赖于桥接间隔物。电位差(ΔE1/2)和比例常数(Kc)随乙烯基单元长度的增加而减小。由单电子氧化生成的混合价态物质在近红外(NIR)区有吸收。此外,FTIR研究还揭示了混合价态的\(\bar{\upsilon }\) (Ru-C≡C)伸展频率的变化,表明桥接配体在氧化还原过程中有相当大的参与。通过改变乙烯基桥接单元的数目,研究了二乙酰二钌有机金属偶联物的电化学和电子性能。
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来源期刊
Journal of Chemical Sciences
Journal of Chemical Sciences CHEMISTRY, MULTIDISCIPLINARY-
CiteScore
3.10
自引率
5.90%
发文量
107
审稿时长
1 months
期刊介绍: Journal of Chemical Sciences is a monthly journal published by the Indian Academy of Sciences. It formed part of the original Proceedings of the Indian Academy of Sciences – Part A, started by the Nobel Laureate Prof C V Raman in 1934, that was split in 1978 into three separate journals. It was renamed as Journal of Chemical Sciences in 2004. The journal publishes original research articles and rapid communications, covering all areas of chemical sciences. A significant feature of the journal is its special issues, brought out from time to time, devoted to conference symposia/proceedings in frontier areas of the subject, held not only in India but also in other countries.
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