Molecular mixed-valence cyanide bridged CoIII-FeII complexes

被引:118
作者
Bernhardt, PV [1 ]
Bozoglián, F
Macpherson, BP
Martínez, M
机构
[1] Univ Queensland, Dept Chem, Brisbane, Qld 4072, Australia
[2] Univ Barcelona, Dept Quim Inorgan, E-08028 Barcelona, Spain
关键词
mixed-valence compounds; metal-to-metal-charge-transfer band energy; outer-sphere oxidation;
D O I
10.1016/j.ccr.2004.11.014
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Cyano-bridged mixed-valence compounds have been known for a long time, i.e., Prussian Blue polymeric solids. Nevertheless, the interest in discrete complexes having a well-defined molecular nuclearity has emerged more recently. There are numerous examples of cyano-bridged mixed-valence complexes in the recent literature, as they show promising and useful applications in electrochromism, molecular magnetism and molecular electronics. In this paper, the reactivity, synthetic and structural chemistry, as well as some physical and chemical properties, of a series of discrete dinuclear mixed-valence cyano-bridged complexes of general formulae [LnCoIII(mu NC)Fe-II(CN)(5)](-) (L = pentadentate macrocyclic ligand) are reviewed. Special emphasis is given to the synthetic strategy, redox properties and metal-to-metal-charge-transfer (MMCT) band energy. Tuning the MMCT transition energy has been possible by changing the redox potential of the metal centers, both through structural and outer-sphere changes. The redox processes that involve the appearance and disappearance of these MMCT bands in the visible region have been dealt with in relation to the possible uses of the complexes. (c) 2004 Elsevier B.V. All rights reserved.
引用
收藏
页码:1902 / 1916
页数:15
相关论文
共 86 条
[1]  
ADAMSON AW, 1963, INORG CHEM, V2, P129
[2]  
Allen G.C., 1967, PROGR INORG CHEM, V8, P357, DOI DOI 10.1002/9780470166093.CH6
[3]   Mixed-valence cyanopyridine-bridged complexes of pentacyanoferrate and pentaammineruthenium: Electronic structure, stability, and redox reactivity [J].
Almaraz, AE ;
Gentil, LA ;
Baraldo, LM ;
Olabe, JA .
INORGANIC CHEMISTRY, 1996, 35 (26) :7718-7727
[4]   OXIDATION OF WATER BY COBALTIC AQUO IONS [J].
ANBAR, M ;
PECHT, I .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1967, 89 (11) :2553-&
[5]   Variable temperature and pressure study of the aquation reactions of cobalt(III) and chromium(III) penta- and tetra-amines [J].
Benzo, F ;
Bernhardt, PV ;
González, G ;
Martinez, M ;
Sienra, B .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1999, (22) :3973-3979
[6]   The first structurally characterized discrete dinuclear μ-cyano hexacyanoferrate complex [J].
Bernhardt, PV ;
Martinez, M .
INORGANIC CHEMISTRY, 1999, 38 (03) :424-+
[7]   Electrochemistry of macrocyclic cobalt(III/II) hexaamines: Electrocatalytic hydrogen evolution in aqueous solution [J].
Bernhardt, PV ;
Jones, LA .
INORGANIC CHEMISTRY, 1999, 38 (22) :5086-5090
[8]   Discrete dinuclear cyano-bridged complexes [J].
Bernhardt, PV ;
Macpherson, BP ;
Martinez, M .
INORGANIC CHEMISTRY, 2000, 39 (23) :5203-5208
[9]   Tuning the metal-to-metal charge transfer energy of cyanobridged dinuclear complexes [J].
Bernhardt, PV ;
Bozoglian, F ;
Macpherson, BP ;
Martinez, M .
DALTON TRANSACTIONS, 2004, (16) :2582-2587
[10]   Discrete cyanide-bridged mixed-valence Co/Fe complexes:: Outer-sphere redox behaviour [J].
Bernhardt, PV ;
Bozoglian, F ;
Macpherson, BP ;
Martínez, M ;
González, G ;
Sienra, B .
EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2003, (13) :2512-2518