Molecular aggregates between octaethyltetrathiaporphyrin dication (OTP2+) and octaethylporphyrin (H2OEP) and its metal complexes

Atif Mahammed; Mordecai Rabinovitz; Roy E. Hoffman; Itamar Willner; Emanuel Vogel; Michael Pohl

doi:10.1002/poc.610081005

Molecular aggregates between octaethyltetrathiaporphyrin dication (OTP²⁺) and octaethylporphyrin (H₂OEP) and its metal complexes

Atif Mahammed
, Mordecai Rabinovitz
, Roy E. Hoffman
, Itamar Willner^*
, Emanuel Vogel
, Michael Pohl

^*Corresponding author for this work

Institute of Chemistry

Research output: Contribution to journal › Article › peer-review

Abstract

The octaethyltetrathiaporphyrin dication, OTP²⁺, forms 1:1 intermolecular donor–acceptor complexes with Ni^II‐, V^IVO‐ and Fe^III‐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 E_a = 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.

Original language	English
Pages (from-to)	659-670
Number of pages	12
Journal	Journal of Physical Organic Chemistry
Volume	8
Issue number	10
DOIs	https://doi.org/10.1002/poc.610081005
State	Published - Oct 1995

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@article{ef4a17fcc22b4aa191fe4fd5f692b046,

title = "Molecular aggregates between octaethyltetrathiaporphyrin dication (OTP2+) and octaethylporphyrin (H2OEP) and its metal complexes",

abstract = "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.",

author = "Atif Mahammed and Mordecai Rabinovitz and Hoffman, \{Roy E.\} and Itamar Willner and Emanuel Vogel and Michael Pohl",

year = "1995",

month = oct,

doi = "10.1002/poc.610081005",

language = "אנגלית",

volume = "8",

pages = "659--670",

journal = "Journal of Physical Organic Chemistry",

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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.

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Molecular aggregates between octaethyltetrathiaporphyrin dication (OTP²⁺) and octaethylporphyrin (H₂OEP) and its metal complexes

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