Syntheses and investigation of the effects of position and nature of substituent on the spectral, electrochemical and spectroelectrochemical properties of new cobalt phthalocyanine complexes

被引：54

作者：

Akinbulu, Isaac Adebayo ^{[1
]}

Nyokong, Tebello ^{[1
]}

机构：

[1] Rhodes Univ, Dept Chem, ZA-6140 Grahamstown, South Africa

来源：

POLYHEDRON | 2010年 / 29卷 / 04期

基金：

新加坡国家研究基金会;

关键词：

Cobalt; Diethylaminoethanethiol phthalocyanine; Benzylmercapto phthalocyanine; Cyclic voltammetry; Spectroelectrochemisrty;

D O I：

10.1016/j.poly.2010.01.004

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The syntheses of new cobalt phthalocyanine (CoPc) complexes, tetra-substituted with diethylaminoethanethio at the peripheral (complex 3a) and non-peripheral (complex 3b) positions, and with benzylmercapto at the non-peripheral position (complex 5), are reported. The effects of the nature and position of substituent on the spectral, electrochemical and spectroelectrochemical properties of these complexes are investigated. Solution electrochemistry of complex 3a showed three distinctly resolved redox processes attributed to (CoPc-2)-Pc-III/(CoPc-2)-Pc-II (E-1/2 = +0.64 V versus Ag|AgCl), (CoPc-2)-Pc-II/(CoPc-2)-Pc-I (E-1/2 = -0.24 V versus Ag|AgCl) and (CoPc-2)-Pc-I/(CoPc-3)-Pc-I (E-1/2 = -1.26 V versus Ag|AgCl) species. No ring oxidation was observed in complex 3a. Complex 3b showed both ring-based oxidation, attributed to (CoPc-1)-Pc-III/(CoPc-2)-Pc-III species (E-p = +0.86 V versus Ag|AgCl), and ring-based reduction associated with (CoPc-2)-Pc-I/(CoPc-3)-Pc-I species (E-1/2 = -1.46 V versus Ag|AgCl), with the normal metal-based redox processes in CoPc complexes: (CoPc-2)-Pc-III/(CoPc-2)-Pc-II (E-p = +0.41 V versus Ag|AgCl) and CouPc-2/ColPc-2 (E-1/2 = -0.38 V versus Ag|AgCl). Solution electrochemistry of complex 5 showed the same type and number of species observed in complex 3a: (CoPc-2)-Pc-III/(CoPc-2)-Pc-II (E-p = +0.59 V versus Ag|AgCl), (CoPc-2)-Pc-II/(CoPc-2)-Pc-I (E-1/2 = -0.26 V versus Ag|AgCl) and (CoPc-2)-Pc-I/(CoPc-3)-Pc-I (E-1/2 = -1.39 V versus Ag|AgCl) species. These processes were confirmed using spectroelectrochemistry. (C) 2010 Elsevier Ltd. All rights reserved.

引用

页码：1257 / 1270

页数：14

共 20 条

[1] SYNTHESIS AND STRUCTURAL STUDIES OF METAL(II) 4,9,16,23-PHTHALOCYANINE TETRAAMINES [J].

ACHAR, BN ;

FOHLEN, GM ;

PARKER, JA ;

KESHAVAYYA, J .

POLYHEDRON, 1987, 6 (06) :1463-1467

[2] Synthesis and electrochemical properties of benzyl-mercapto and dodecyl-mercapto tetrasubstituted manganese phthalocyanine complexes [J].

Agboola, Bolade ;

Ozoemena, Kenneth I. ;

Westbroek, Philippe ;

Nyokong, Tebello .

ELECTROCHIMICA ACTA, 2007, 52 (07) :2520-2526

[3] Synthesis and electrochemical characterisation of benzylmercapto and dodecylmercapto tetra substituted cobalt, iron, and zinc phthalocyanines complexes [J].

Agboola, Bolade ;

Ozoemena, Kenneth I. ;

Nyokong, Tebello .

ELECTROCHIMICA ACTA, 2006, 51 (21) :4379-4387

[4]

AKINBULU IA, 2009, POLYHEDRON, V28, P2831

[5] Synthesis and characterization of novel soluble octa-cationic phthalocyanines [J].

Bayir, ZA .

DYES AND PIGMENTS, 2005, 65 (03) :235-242

[6] Electrocatalytic oxidation of nitrite on a vitreous carbon electrode modified with cobalt phthalocyanine [J].

Caro, CA ;

Bedioui, F ;

Zagal, JH .

ELECTROCHIMICA ACTA, 2002, 47 (09) :1489-1494

[7] Conformationally stressed phthalocyanines: the non-planarity of the 1,4,8,11,15,18,22,25-octaisopentyl derivative [J].

Chambrier, I ;

Cook, MJ ;

Wood, PT .

CHEMICAL COMMUNICATIONS, 2000, (21) :2133-2134

[8] SYNTHESIS AND SPECTROSCOPIC PROPERTIES OF SYMMETRICALLY TETRASUBSTITUTED PHTHALOCYANINES WITH 4 ALKYL OR ARYL CHAINS OR PORPHYRIN, ADAMANTANE, CROWN, OR QUINONE UNITS ATTACHED [J].

KOBAYASHI, N ;

OHYA, T ;

SATO, M ;

NAKAJIMA, S .

INORGANIC CHEMISTRY, 1993, 32 (09) :1803-1808

[9]

Lever A.B. P., 1993, PHTHALOCYANINES PROP, V3, P1, DOI DOI 10.1039/C2CC31167D

[10]

Leznoff C.C., 1989, PHTHALOCYANINES, P1

← 1 2 →