Issue 40, 2012
From the journal:

Dalton Transactions

Synthesis and ECL performance of highly efficient bimetallic ruthenium tris-bipyridyl complexes†

Shiguo Sun,*a   Fusheng Li,a   Fengyu Liu,b   Xue Yang,b   Jiangli Fan,a   Fengling Song,a   Licheng Sun*c  and  Xiaojun Peng*a  

* Corresponding authors

a State Key Laboratory of Fine Chemicals, Dalian University of Technology, E 224 West Campus, No. 2, Linggonglu, Gangjingzi District, Dalian, China
E-mail: shiguo@dlut.edu.cn, pengxj@dlut.edu.cn
Fax: +86 411 84986304
Tel: +86 411 84986304

b School of Chemistry, Dalian University of Technology, No. 2, Linggonglu, Ganjingzi District, Dalian, China

c Department of Chemistry, Organic Chemistry, School of Chemical Science and Engineering, Royal Institute of Technology (KTH), Teknikringen 30, S-100 44 Stockholm, Sweden
E-mail: lichengs@ kth.se

Abstract

In order to find the ideal carbon chain linkage number n for achieving the highest ECL in bimetallic ruthenium tris-bipyridyl complexes, a series of novel complexes [(bpy)2Ru(bpy′)(CH2)n(bpy′)Ru(bpy)2]4+ (1, where bpy is 2,2′-bipyridyl, n = 10, 12, 14) for a coreactant electrochemiluminescence (ECL) system have been synthesized. Their ECL properties at a Au electrode have been studied in 0.1 M phosphate buffer by using tripropylamine (TPrA), 2-(dibutylamino)ethanol (DBAE) and melamine as the coreactant, to compare with that of the previously reported bimetallic ruthenium analogous complex [(bpy)2Ru(bpy′)(CH2)8(bpy′)Ru(bpy)2]4+. The results demonstrate that the ECL intensity depends largely on the length of the saturated carbon chain linkage number n. The highest ECL is reached when n = 10, suggesting that a synergistic effect on ECL enhancement co-exists between the two intramolecular linked ruthenium activating centers. Density functional theory (DFT) calculation demonstrated that the optimized bond distances between Ru and N(bpy′) are the longest both in the ground and the excited triplet states in the case of n = 10, while those for Ru and N(bpy) are the shortest in the excited triplet states. All these factors may be responsible for the above mentioned results. This study provided a methodology to further improve and tune ECL efficiency by using bimetallic ruthenium complexes linked by a flexible saturated carbon chain.

Graphical abstract: Synthesis and ECL performance of highly efficient bimetallic ruthenium tris-bipyridyl complexes

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Article information

DOI
https://doi.org/10.1039/C2DT31603J
Article type
Paper
Submitted
19 Jul 2012
Accepted
15 Aug 2012
First published
20 Aug 2012

Dalton Trans., 2012,41, 12434-12438

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Synthesis and ECL performance of highly efficient bimetallic ruthenium tris-bipyridyl complexes

S. Sun, F. Li, F. Liu, X. Yang, J. Fan, F. Song, L. Sun and X. Peng, Dalton Trans., 2012, 41, 12434 DOI: 10.1039/C2DT31603J

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