APPLICATION OF TRANSIENT RESONANCE RAMAN-SPECTROSCOPY TO THE STRUCTURE OF A PHOTOINDUCED ELECTRON-TRANSFER INTERMEDIATE

被引：53

作者：

SCHOONOVER, JR ^{[1
]}

CHEN, PY ^{[1
]}

BATES, WD ^{[1
]}

DYER, RB ^{[1
]}

MEYER, TJ ^{[1
]}

机构：

[1] UNIV N CAROLINA, DEPT CHEM, CHAPEL HILL, NC 27599 USA

来源：

INORGANIC CHEMISTRY | 1994年 / 33卷 / 04期

关键词：

D O I：

10.1021/ic00082a028

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Transient resonance Raman spectra have been acquired for the chromophore-quencher complexes fac-[(bpy)-Re(I)(CO)3(MQ+)]2+ and cis-[(bpy)2Os(II)(CO)(MQ+)]3+ (MQ+ is monoquat, N-methyl-4,4'-bipyridinium cation; bpy is 2,2'-bipyridine) following metal-to-ligand charge-transfer excitation. The transient spectra verify that bpy.- --> MQ+ intramolecular electron transfer occurs (tau < 7 ns) with the excited electron residing ultimately on the monoquat ligand. By comparison to vibrational data for biphenyl, 4,4'-bipyridine, N,N'-dihydro-4,4'-bipyridinium dication, and methyl viologen (paraquat) and their corresponding, one-electron reduced forms, it can be inferred that, in the MQ+-based MLCT excited state, the electron is delocalized over the entire ligand and the two pyridyl rings assume a coplanar geometry.

引用

页码：793 / 797

页数：5

共 64 条

[1] STRUCTURE AND BARRIER OF INTERNAL-ROTATION OF BIPHENYL DERIVATIVES IN THE GASEOUS STATE .1. THE MOLECULAR-STRUCTURE AND NORMAL COORDINATE ANALYSIS OF NORMAL BIPHENYL AND PERDEUTERATED BIPHENYL [J].

ALMENNINGEN, A ;

BASTIANSEN, O ;

FERNHOLT, L ;

CYVIN, BN ;

CYVIN, SJ ;

SAMDAL, S .

JOURNAL OF MOLECULAR STRUCTURE, 1985, 128 (1-3) :59-76

[2] CHARACTERIZATION OF METAL-TO-LIGAND CHARGE-TRANSFER AND INTRALIGAND TRANSITIONS OF FAC-[RE(CO)3L(X)] COMPLEXES [L=DI-IMINE - X=HALIDE OR MN(CO)5] AND EXPLANATION OF THE PHOTOCHEMISTRY OF [RE(CO)3L-[MN(CO)5]] USING THE RESONANCE RAMAN EFFECT [J].

BALK, RW ;

STUFKENS, DJ ;

OSKAM, A .

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1981, (05) :1124-1133

[3]

BALZANI V, 1991, SUPRAMOLECULAR PHOTO

[4] RESONANCE RAMAN-SPECTRA OF THE N,N-DIHYDRO-4,4'-BIPYRIDINIUM RADICAL CATION [J].

BARKER, DJ ;

COONEY, RP ;

SUMMERS, LA .

JOURNAL OF RAMAN SPECTROSCOPY, 1987, 18 (06) :443-445

[5] STRUCTURE AND BARRIER OF INTERNAL-ROTATION OF BIPHENYL DERIVATIVES IN THE GASEOUS STATE .4. BARRIER OF INTERNAL-ROTATION IN BIPHENYL, PERDEUTERATED BIPHENYL AND 7 NON-ORTHO-SUBSTITUTED HALOGEN-DERIVATIVES [J].

BASTIANSEN, O ;

SAMDAL, S .

JOURNAL OF MOLECULAR STRUCTURE, 1985, 128 (1-3) :115-125

[6] LONG-RANGE ENERGY-TRANSFER IN OLIGOMERIC METAL-COMPLEX ASSEMBLIES [J].

BIGNOZZI, CA ;

ARGAZZI, R ;

GARCIA, CG ;

SCANDOLA, F ;

SCHOONOVER, JR ;

MEYER, TJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1992, 114 (22) :8727-8729

[7] VIBRATIONAL SPECTROSCOPY OF THE ELECTRONICALLY EXCITED-STATE .5. TIME-RESOLVED RESONANCE RAMAN-STUDY OF TRIS(BIPYRIDINE)RUTHENIUM(II) AND RELATED COMPLEXES - DEFINITIVE EVIDENCE FOR THE LOCALIZED MLCT STATE [J].

BRADLEY, PG ;

KRESS, N ;

HORNBERGER, BA ;

DALLINGER, RF ;

WOODRUFF, WH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (25) :7441-7446

[8]

CARSON SL, 1992, J AM CHEM SOC, V114, P9504

[9] RESONANCE RAMAN-SPECTRA OF THE GROUND AND CHARGE-TRANSFER EXCITED-STATE OF PENTAAMMINE(4,4'-BIPYRIDINE)RUTHENIUM(II) AND PENTAAMMINE(4,4'-BIPYRIDINIUM)RUTHENIUM(II) [J].

CASWELL, DS ;

SPIRO, TG .

INORGANIC CHEMISTRY, 1987, 26 (01) :18-22

[10]

Chanon M., 1988, PHOTOINDUCED ELECTRO

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