Modeling the bonding changes in chlorophyll cation radicals: Resonance Raman spectroscopy of nickel(II) methyl pyropheophorbide a

被引:7
作者
Lin, CY
McGlashen, ML
Hu, SZ
Shim, YK
Smith, KM
Spiro, TG
机构
[1] PRINCETON UNIV,DEPT CHEM,PRINCETON,NJ 08544
[2] UNIV CALIF DAVIS,DEPT CHEM,DAVIS,CA 95616
关键词
chlorophylls; nickel complexes; nickel methyl pyropheophorbide a complexes;
D O I
10.1016/S0020-1693(96)05312-1
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Electrochemistry, UV-Vis absorption and resonance Raman (RR) spectra are reported for nickel methyl pyropheophorbide a (NiMPPh) and its cation radical, in order to help understand the structural changes upon oxidation in chlorophyll cation radicals. RR band shifts, and also the oxidation potential, are consistent with the highest occupied molecular orbital (HOMO) of NiMPPh being an A(1u)-like orbital, which interacts with the keto-carbonyl group on the isocyclic ring. Of particular interest is the upshift of the keto-carbonyl stretching mode in the NiMPPh cation radical. The strengthening of the carbonyl bond upon oxidation is consistent with the expected anti-bonding character of the A(1u)-like orbital with respect to the keto C=O bond.
引用
收藏
页码:179 / 184
页数:6
相关论文
共 46 条
[1]   SPECTROSCOPIC ANALYSIS OF CHLOROPHYLL MODEL COMPLEXES - METHYL-ESTER C1FE(III)PHEOPHORBIDES [J].
ANDERSSON, LA ;
LOEHR, TM ;
COTTON, TM ;
SIMPSON, DJ ;
SMITH, KM .
BIOCHIMICA ET BIOPHYSICA ACTA, 1989, 974 (02) :163-179
[2]   CHLOROPHYLL MODEL COMPOUNDS - EFFECTS OF LOW SYMMETRY ON THE RESONANCE RAMAN-SPECTRA AND NORMAL MODE DESCRIPTIONS OF NICKEL(II) DIHYDROPORPHYRINS [J].
BOLDT, NJ ;
DONOHOE, RJ ;
BIRGE, RR ;
BOCIAN, DF .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (08) :2284-2298
[3]   ASSIGNMENT OF BACTERIOCHLOROPHYLL-ALPHA LIGATION STATE FROM ABSORPTION AND RESONANCE RAMAN-SPECTRA [J].
CALLAHAN, PM ;
COTTON, TM .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (23) :7001-7007
[4]   RESONANCE RAMAN-SPECTRA OF BACTERIOCHLOROPHYLL AND ITS ELECTROGENERATED CATION RADICAL - EXCITATION OF THE SORET BANDS BY USE OF STIMULATED RAMAN-SCATTERING FROM H-2 AND D2 [J].
COTTON, TM ;
PARKS, KD ;
VANDUYNE, RP .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1980, 102 (21) :6399-6407
[5]   CHARACTERIZATION OF BACTERIOCHLOROPHYLL INTERACTIONS INVITRO BY RESONANCE RAMAN-SPECTROSCOPY [J].
COTTON, TM ;
VANDUYNE, RP .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1981, 103 (20) :6020-6026
[6]   RESONANCE RAMAN SPECTROELECTROCHEMISTRY OF BACTERIOCHLOROPHYLL AND BACTERIOCHLOROPHYLL CATION RADICAL [J].
COTTON, TM ;
VANDUYNE, RP .
BIOCHEMICAL AND BIOPHYSICAL RESEARCH COMMUNICATIONS, 1978, 82 (02) :424-433
[7]   RESONANCE RAMAN-SPECTROSCOPY REVEALS A1U VS A2U CHARACTER AND PSEUDO-JAHN-TELLER DISTORTION IN RADICAL CATIONS OF NIII, CUII, AND CLFEIII OCTAETHYLPORPHYRINS AND TETRAPHENYLPORPHYRINS [J].
CZERNUSZEWICZ, RS ;
MACOR, KA ;
LI, XY ;
KINCAID, JR ;
SPIRO, TG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (11) :3860-3869
[9]   RESONANCE RAMAN-SPECTRA OF THE ANION AND CATION RADICALS OF BACTERIAL PHOTOSYNTHETIC PIGMENTS [J].
DIERS, JR ;
BOCIAN, DF .
JOURNAL OF PHYSICAL CHEMISTRY, 1994, 98 (49) :12884-12892
[10]   NEAR-INFRARED-EXCITATION RESONANCE RAMAN-SPECTRA OF THE PRIMARY ELECTRON-DONOR IN PHOTOSYNTHETIC REACTION CENTERS FROM RHODOBACTER-SPHAEROIDES [J].
DONOHOE, RJ ;
DYER, RB ;
SWANSON, BI ;
VIOLETTE, CA ;
FRANK, HA ;
BOCIAN, DF .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1990, 112 (18) :6716-6718