Conducting polymers containing in-chain metal centers:: Electropolymerization of oligothienyl-substituted {M(tpy)2} complexes and in situ conductivity studies, M = Os(II), Ru(II)

被引:97
作者
Hjelm, J
Handel, RW
Hagfeldt, A
Constable, EC
Housecroft, CE
Forster, RJ
机构
[1] Univ Basel, Dept Chem, CH-4056 Basel, Switzerland
[2] Uppsala Univ, Dept Phys Chem, SE-75123 Uppsala, Sweden
[3] Dublin City Univ, Natl Ctr Sensor Res, Dublin 9, Ireland
关键词
D O I
10.1021/ic049221m
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The electropolymerization of a series of Ru and Os bis-terpyridine complexes that form rodlike polymers with bithienyl, quaterthienyl, or hexathienyl bridges has been studied. Absorption spectroscopy, scanning electron microscopy, and cyclic voltammetry have been used to characterize the monomers and resulting polymer films. The absolute dc conductivity of the quaterthienyl-bridged {Ru(tpy)(2)} and {Os(tpy)(2)} polymers is unusually large and independent of the identity of the metal center at 1.6 x 10(-3) S cm(-1). The maximum conductivity occurs at the formal potential of each redox process, which typically is observed for systems where redox conduction is the dominant charge transport mechanism. Significantly, the dc conductivity of the metal-based redox couple observed in these polymers is 2 orders of magnitude higher than that of a comparable nonconjugated system.
引用
收藏
页码:1073 / 1081
页数:9
相关论文
共 43 条
[1]   RECTIFYING INTERFACES USING 2-LAYER FILMS OF ELECTROCHEMICALLY POLYMERIZED VINYLPYRIDINE AND VINYLBIPYRIDINE COMPLEXES OF RUTHENIUM AND IRON ON ELECTRODES [J].
ABRUNA, HD ;
DENISEVICH, P ;
UMANA, M ;
MEYER, TJ ;
MURRAY, RW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (01) :1-5
[2]   Enantiomerically pure chiral coordination polymers:: Synthesis, spectroscopy, and electrochemistry in solution and on surfaces [J].
Bernhard, S ;
Takada, K ;
Díaz, DJ ;
Abruña, HD ;
Mürner, H .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (42) :10265-10271
[3]   Metal-metal interactions in a novel hybrid metallopolymer [J].
Cameron, CG ;
Pickup, PG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (50) :11773-11779
[4]   REDOX CAPACITY AND DIRECT-CURRENT ELECTRON CONDUCTIVITY IN ELECTROACTIVE MATERIALS [J].
CHIDSEY, CED ;
MURRAY, RW .
JOURNAL OF PHYSICAL CHEMISTRY, 1986, 90 (07) :1479-1484
[5]   Efficient syntheses of 4′-(2-thienyl)- and 4′-(3-thienyl)-2,2′:6′, 2"-terpyridine:: preparation and characterization of Fe(II), Ru(II), Os(II) and Co(II) complexes [J].
Constable, EC ;
Handel, R ;
Housecroft, CE ;
Neuburger, M ;
Schofield, ER ;
Zehnder, M .
POLYHEDRON, 2004, 23 (01) :135-143
[6]  
CONSTABLE EC, 1992, NEW J CHEM, V16, P855
[7]   UNIDIRECTIONAL CURRENT FLOW AND CHARGE STATE TRAPPING AT REDOX POLYMER INTERFACES ON BILAYER ELECTRODES - PRINCIPLES, EXPERIMENTAL DEMONSTRATION, AND THEORY [J].
DENISEVICH, P ;
WILLMAN, KW ;
MURRAY, RW .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (16) :4727-4737
[8]  
Encinas S, 2002, CHEM-EUR J, V8, P137, DOI 10.1002/1521-3765(20020104)8:1<137::AID-CHEM137>3.0.CO
[9]  
2-X
[10]   ELECTROCHEMISTRY OF SPONTANEOUSLY ADSORBED MONOLAYERS - EQUILIBRIUM PROPERTIES AND FUNDAMENTAL ELECTRON-TRANSFER CHARACTERISTICS [J].
FORSTER, RJ ;
FAULKNER, LR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1994, 116 (12) :5444-5452