Reactivity descriptors applied to the study of cobalt porphyrin and their aza derivatives

被引:20
作者
Cárdenas-Jirón, GI [1 ]
机构
[1] Univ Santiago Chile, Fac Quim & Biol, Dept Ciencias Quim, Santiago, Chile
关键词
cobalt; porphyrin; Fukui; hardness; reactivity; density functional;
D O I
10.1002/qua.10443
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
A theoretical study at the density functional level of theory (ROBLYP/3-21G*) of the reactivity of cobalt porphyrin (CoP) and their aza derivatives (CoP(xN)) by using global and local indexes is presented. First, vertical ionization potentials and electronic affinities are calculated to determine global reactivity descriptors such as the chemical potential (mu), molecular hardness (eta), and electrophilicity (omega). In general, it is found that eta and omega increase with the inclusion of aza-N atoms in the cobalt porphyrin. The cobalt condensed Fukui function (f(Co)) and cobalt condensed electrostatic potential (EPCo) for the set of CoP(xN) are also determined. We obtained that f(Co)(-) decreases with the increase of aza-N atoms, which indicates that a minimum Fukui function is preferred for hard-hard interactions, in agreement with previous results (Cardenas-jiron, G. J. J Phys Chem A 2002, 106, 3202). Results obtained for EPCo indicates that the increase of aza-N atoms leads to a more electrophilic site for the cobalt atom that is also stated at a global level through the results of omega, which are referred to the molecule as a whole. It is concluded that global and local descriptors are complementary in this reactivity study and both give enough information to rationalize the effect of the inclusion of aza-N atoms in the porphyrin upon the reactivity. (C) 2002 Wiley Periodicals, Inc.
引用
收藏
页码:389 / 397
页数:9
相关论文
共 54 条
[1]   Large molecular hyperpolarizabilities in "push-pull" porphyrins. Molecular planarity and auxiliary donor-acceptor effects [J].
Albert, IDL ;
Marks, TJ ;
Ratner, MA .
CHEMISTRY OF MATERIALS, 1998, 10 (03) :753-762
[2]   Variational principles for describing chemical reactions: The Fukui function and chemical hardness revisited [J].
Ayers, PW ;
Parr, RG .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (09) :2010-2018
[3]   ORIENTATION CHANGE OF DIMER-TYPE PORPHYRIN IN LANGMUIR-BLODGETT-FILMS CAUSED BY A TRIGGER MOLECULE [J].
AZUMI, R ;
MATSUMOTO, M ;
KURODA, S ;
KING, LG ;
CROSSLEY, MJ .
LANGMUIR, 1995, 11 (10) :4056-4060
[4]   Solvent effect on the global and atomic DFT-based reactivity descriptors using the effective fragment potential model. Solvation of ammonia [J].
Balawender, R ;
Safi, B ;
Geerlings, P .
JOURNAL OF PHYSICAL CHEMISTRY A, 2001, 105 (27) :6703-6710
[5]   ADVANCES IN PHOTOCHEMICAL APPROACHES FOR BLOOD STERILIZATION [J].
BENHUR, E ;
HOROWITZ, B .
PHOTOCHEMISTRY AND PHOTOBIOLOGY, 1995, 62 (03) :383-388
[6]   DENSITY FUNCTIONAL-APPROACH TO FRONTIER CONTROLLED REACTIONS [J].
BERKOWITZ, M .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (16) :4823-4825
[7]  
BONNETT R, 1995, CHEM SOC REV, V19
[8]   PORPHYRIN SPONGES - STRUCTURAL SYSTEMATICS OF THE HOST LATTICE [J].
BYRN, MP ;
CURTIS, CJ ;
GOLDBERG, I ;
HSIOU, Y ;
KHAN, SI ;
SAWIN, PA ;
TENDICK, SK ;
STROUSE, CE .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1991, 113 (17) :6549-6557
[9]   Theoretical study of the interaction energy profile of cobalt phthalocyanine and 2-mercaptoethanol.: Effect of the graphite on the global reactivity [J].
Cárdenas-Jirón, GI ;
Caro, CA ;
Venegas-Yazigi, D ;
Zagal, JH .
JOURNAL OF MOLECULAR STRUCTURE-THEOCHEM, 2002, 580 :193-200
[10]   Substituent effect in the chemical reactivity and selectivity of substituted cobalt phthalocyanines [J].
Cárdenas-Jirón, GI .
JOURNAL OF PHYSICAL CHEMISTRY A, 2002, 106 (13) :3202-3206