TY - JOUR
T1 - Molecular aggregates between octaethyltetrathiaporphyrin dication (OTP2+) and octaethylporphyrin (H2OEP) and its metal complexes
AU - Mahammed, Atif
AU - Rabinovitz, Mordecai
AU - Hoffman, Roy E.
AU - Willner, Itamar
AU - Vogel, Emanuel
AU - Pohl, Michael
PY - 1995/10
Y1 - 1995/10
N2 - The octaethyltetrathiaporphyrin dication, OTP2+, forms 1:1 intermolecular donor–acceptor complexes with NiII‐, VIVO‐ and FeIII‐octaethylporphyrins. The association constants of the complexes are governed by the oxidation potential of the metallo‐octaethylporphyrins and by secondary electrostatic interactions. Octaethylporphyrin, H2OEP, forms intermolecular complexes with OTP2+. Kinetic analyses of the formation of the various complexes revealed the formation of a primary complex exhibiting the stoichiometry (OTP2+)2(H2OEP). This intermolecular complex transforms into a thermodynamically stabilized intermolecular assembly with a stoichiometry corresponding to (OTP2+)4H2OEP. The activation barrier associated with the conversion of the primary complex to the thermodynamically stabilized assembly is Ea = 16·5 kcal mol−1 (1 kcal = 4·184 kJ). The association constant of the complex (OTP2+)2(H2OEP) is K1 = 1·3 × 1010 M−2 and the equilibrium constant between the two coexisting intermolecular complexes (OTP2+)4(H2OEP) and (OTP2+)2(H2OEP) is K2 = 7·4.
AB - The octaethyltetrathiaporphyrin dication, OTP2+, forms 1:1 intermolecular donor–acceptor complexes with NiII‐, VIVO‐ and FeIII‐octaethylporphyrins. The association constants of the complexes are governed by the oxidation potential of the metallo‐octaethylporphyrins and by secondary electrostatic interactions. Octaethylporphyrin, H2OEP, forms intermolecular complexes with OTP2+. Kinetic analyses of the formation of the various complexes revealed the formation of a primary complex exhibiting the stoichiometry (OTP2+)2(H2OEP). This intermolecular complex transforms into a thermodynamically stabilized intermolecular assembly with a stoichiometry corresponding to (OTP2+)4H2OEP. The activation barrier associated with the conversion of the primary complex to the thermodynamically stabilized assembly is Ea = 16·5 kcal mol−1 (1 kcal = 4·184 kJ). The association constant of the complex (OTP2+)2(H2OEP) is K1 = 1·3 × 1010 M−2 and the equilibrium constant between the two coexisting intermolecular complexes (OTP2+)4(H2OEP) and (OTP2+)2(H2OEP) is K2 = 7·4.
UR - http://www.scopus.com/inward/record.url?scp=84985453628&partnerID=8YFLogxK
U2 - 10.1002/poc.610081005
DO - 10.1002/poc.610081005
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AN - SCOPUS:84985453628
SN - 0894-3230
VL - 8
SP - 659
EP - 670
JO - Journal of Physical Organic Chemistry
JF - Journal of Physical Organic Chemistry
IS - 10
ER -