Molecular recognition of NO/NO+ via multicenter (charge-transfer) binding to bridged diarene donors. Effect of structure on the optical transitions and complexation thermodynamics.
Bridged diarenes form very strong [1:1] complexes with nitrosonium/nitric oxide in which the NO moiety is optimally sandwiched in the cleft between a pair of cofacial aromatic rings which act as a molecular "Venus flytrap". The spectral features of these associates are generally similar to those for [1:1] and [2:1] nitrosonium complexes with mononuclear alkyl-substituted benzenes, and they are appropriately described within the LCAO molecular-orbital methodology and the Mulliken (charge-transfer) formulation of donor/acceptor electronic transitions. The thermodynamics study indicates that the efficient binding is determined by (i) the close matching of the donor/acceptor redox potentials and (ii) the ability of bridged diarenes for multicentered interactions with a single NO moiety. The best fit of the electronic and structural parameters is provided by a calixarene host that allows the interacting centers to be arranged in a manner similar to those extant in [2:1] nitrosonium complexes with analogous (nonbridged) aromatic donors; this results in its very strong noncovalent binding with nitrosonium/nitric oxide with the formation constant of K(B) approximately 10(8) M(-)(1) and free-energy change of -DeltaG degrees = 45 kJ mol(-)(1). Such strong, selective, and reversible bindings of nitrosonium/nitric oxide by (cofacial) aromatic centers thus provide the basis for the development of efficient NO sensors/absorbents and also suggest their potential relevance to biochemical systems.
University of Houston, Chemistry Department, Texas 77204, USA.
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Rosokha
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Lindeman
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Rathore
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Kochi