Ionic interactions in the oligoviologens-K4Fe(CN)6 system

被引：2
|
作者：
Zhidkova, M. N. [1 ]
Birin, K. P. [2 ]
Laurinavichyute, V. K. [1 ]
Pugolovkin, L. V. [1 ]
Kotov, V. Yu. [3 ,4 ]
机构：
[1] Moscow MV Lomonosov State Univ, Fac Chem, Moscow 119991, Russia
[2] AN Frumkin Inst Phys Chem & Electrochem RAS, Moscow 119071, Russia
[3] NS Kurnakov Gen & Inorgan Chem Inst RAS, Moscow 119071, Russia
[4] RAS, Higher Chem Coll, Moscow 125047, Russia
来源：
JOURNAL OF ELECTROANALYTICAL CHEMISTRY | 2016年 / 773卷
关键词：
Oligoviologens; Menshutkin reaction; 1H NMR; Inner- and outer-sphere complexes; Cyclic voltammetry; ELECTROCHEMICAL-BEHAVIOR; VIOLOGEN; ADSORPTION; COMPLEXES; GOLD;
D O I：
10.1016/j.jelechem.2016.04.039
中图分类号：
O65 [分析化学];
学科分类号：
070302 ; 081704 ;
摘要：
Various oligoviologen derivatives were synthesized by Menshutkin reaction of 4,4'-bipyridine (BPy), with alpha,omega-dibromoalkanes (alpha,omega-CnH2nBr2) in acetonitrile medium. 1H NMR analysis demonstrated that the degree of polymerization increases with alkyl chain length and reaction time, reaching its maximum at the molar reagent ratio (alpha,omega-CnH2nBr2/BPy) of 1.2: 1. The obtained oligomers and their interaction with [Fe(CN)(6)](4-) anions were characterized by 1H NMR, cyclic voltammetry, electronic absorption spectroscopy and EDX analysis. Two principally different types of interaction between low molecular weight oligoviologens and hexacyanoferrate ions were established: 1) fast reversible outer-sphere charge transfer complex formation and 2) slow irreversible reaction, presumably corresponding to the inner-sphere complex [Fe(CN)(5)L](q +/-) formation. Oligoviologens with medium molecular weight were found to form a poorly soluble product with [Fe(CN)(6)](4-) ions, which can be redissolved again by the addition of halide ions. (C) 2016 Elsevier B.V. All rights reserved.
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收藏
页码：47 / 52
页数：6
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