Metallophilicity versus π-π Interactions: Argentophilicity in Porphyrin Dimer

Pragati1,, Akhilesh Kumar2,*,, Akhil K. Singh3,, Arvind Kumar Pandey4, and Santosh Kumar Srivastava1,

1Department of Chemistry, C.M.P. Degree College, Pragyagraj-211002, India

2Department of Chemistry, P.B.P.G. College, Prataphgarh-230002, India

3Institute for Inorganic Chemistry, Karlsruhe Institute of Technology, 76131 Karlsruhe, Germany

4Department of Chemistry, University of Allahabad, Pragyagraj-211002, India

*Corresponding author: E-mail: aks.modanwal@gmail.com

Abstract

The interaction between two unsupported Ag(III)porphyrins, which exist as a metalloporphyrin dimer has been studied. The UV-visible spectrum shows only slight change in Soret band position indicative of Ag(III) formation. Optimized structure of the complexes has clearly revealed that only metal-centered oxidation results in short Ag-N (porphyrin) distance with large distortion in the porphyrin macrocycle. The dispersion effect brings two rings more closer to form an unprecedented Ag(III)···Ag(III) interaction and cancel out the π-π repulsion. The interaction energy was found to be 55.34 Kcal/mol and was further supported by electron localization function, AIM analysis. The Ag(III) dimer also gives pink emission at low temperature. This type of interaction can be exploited to design several light responsive materials and molecular semiconductors.

Keywords

Metallophilic interaction, Porphyrin dimer, QTAIM analysis, Electronic structure.

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