Supramolecular effects in redox chemistry. Local solvation in basket-handle iron porphyrins containing an increasing number of secondary amide groups
Local solvation can be created by including dipolar groups in a molecular superstructure attached to a reacting center. Changes in reactivity of the latter ensue in a manner which is reminiscent of the modulation of the reactivity of the prosthetic groups by surrounding protein chains in enzymatic systems. Quite large effects can thus be obtained as shown by an electrochemical study of two redox reactions, Fe(II) + e/sup -/ in equilibrium Fe(I)/sup -/, Fe(I)/sup -/ + e/sup -/ in equilibrium Fe(0)/sup 2 -/, in a series of basket-handle iron prophyrins including an increasing number of secondary amide groups in the chains. The local solvation which results from the electrostatic interaction between the CONH dipoles and the negatively charged porphyrin centers is shown to build up as more and more CONH groups are included and to depend upon the distance between these groups and the reacting center.
- Research Organization:
- l'Universite de Paris, France
- OSTI ID:
- 6538580
- Journal Information:
- J. Phys. Chem.; (United States), Vol. 91:7
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
IRON COMPOUNDS
ELECTROCHEMISTRY
MOLECULAR STRUCTURE
REDOX REACTIONS
ORGANOMETALLIC COMPOUNDS
PORPHYRINS
SOLVATED ELECTRONS
ELECTRIC POTENTIAL
EXPERIMENTAL DATA
CARBOXYLIC ACIDS
CHEMICAL REACTIONS
CHEMISTRY
DATA
ELECTRONS
ELEMENTARY PARTICLES
FERMIONS
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
LEPTONS
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
400400* - Electrochemistry
400201 - Chemical & Physicochemical Properties