Synthesis and solution characterization of [Ru(bpy)2]2+ modified polyazines

被引:4
作者
Cheng, M [1 ]
Euler, WB [1 ]
机构
[1] Univ Rhode Isl, Dept Chem, Kingston, RI 02881 USA
关键词
D O I
10.1021/ic0343049
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A series of [Ru(bpy)(2)](2+) complexes linked by a controlled number of azine units (one to seven) were synthesized and studied in the solution phase. Polymers and dimer model compounds were examined by cyclic voltammetry and IR, NMR, and visible-NIR spectroscopies. The NMR spectra and the cyclic voltammograms indicated that the Ru2+ sites influenced the main chain properties at least 15 Angstrom from the metal site. The first oxidation in each material was assigned to a ligand-centered process, but DFT calculations suggested that the Ru2+ has an important influence. The first oxidized state of the polymers has a spectroscopic band that is consistent with an intervalence transfer (IT) transition, but this absorption is not seen in the dimer model compounds. Thus, the IT feature is assigned to a ligand-ligand transition that spans several repeat units in the polymer.
引用
收藏
页码:5384 / 5391
页数:8
相关论文
共 74 条
[11]   MIXED-VALENCE COMPLEXES OF D5-D6 METAL CENTERS [J].
CREUTZ, C .
PROGRESS IN INORGANIC CHEMISTRY, 1983, 30 :1-73
[12]   Stereochemical influences on intervalence charge transfer in homodinuclear complexes of ruthenium [J].
D'Alessandro, DM ;
Kelso, LS ;
Keene, FR .
INORGANIC CHEMISTRY, 2001, 40 (26) :6841-+
[13]   Conformational gating of long distance electron transfer through wire-like bridges in donor-bridge-acceptor molecules [J].
Davis, WB ;
Ratner, MA ;
Wasielewski, MR .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (32) :7877-7886
[14]   The localized-to-delocalized transition in mixed-valence chemistry [J].
Demadis, KD ;
Hartshorn, CM ;
Meyer, TJ .
CHEMICAL REVIEWS, 2001, 101 (09) :2655-2685
[15]   Direct experimental comparison of the theories of thermal and optical electron-transfer: Studies of a mixed-valence dinuclear iron polypyridyl complex [J].
Elliott, CM ;
Derr, DL ;
Matyushov, DV ;
Newton, MD .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1998, 120 (45) :11714-11726
[16]   Donor/acceptor coupling in mixed-valent dinuclear iron polypyridyl complexes: Experimental and theoretical considerations [J].
Elliott, CM ;
Derr, DL ;
Ferrere, S ;
Newton, MD ;
Liu, YP .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (22) :5221-5228
[17]   Photoinduced two-step energy transfer in a Re/Ru dinuclear complex as mediated by an interposed 'reservoir' unit [J].
Encinas, S ;
Barthram, AM ;
Ward, MD ;
Barigelletti, F ;
Campagna, S .
CHEMICAL COMMUNICATIONS, 2001, (03) :277-278
[18]   Observations implicating vibronic coupling in covalently linked transition metal electron transfer systems [J].
Endicott, JF ;
Watzky, MA ;
Song, XQ ;
Buranda, T .
COORDINATION CHEMISTRY REVIEWS, 1997, 159 :295-323
[19]  
Euler W.B., 1997, HDB ORGANIC CONDUCTI, V2, P719
[20]   IR spectroscopy of pristine and iodine-doped permethylpolyazine [J].
Euler, WB .
CHEMISTRY OF MATERIALS, 1996, 8 (02) :554-557