Open AccessIon-Pair Formation of [CoIII(pn)2(Cl)(L)2+····· I−] by Aqueous-Organic Solvent Medium Enhanced Photoreduction: A Perspective Regression Analysis
Author(s) -
L. Devaraj Stephen,
S. Gunasekaran,
M. Soundarrajan
Publication year - 2020
Publication title -
asian journal of chemistry/asian journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.145
H-Index - 34
eISSN - 0975-427X
pISSN - 0970-7077
DOI - 10.14233/ajchem.2020.22598
Subject(s) - chemistry , solvent , iodide , ion , aqueous solution , catalysis , quantum yield , solvent effects , photochemistry , inorganic chemistry , organic chemistry , physics , quantum mechanics , fluorescence
Reduction of CoIII centre in CoIII(pn)2(Cl)(L)2+ with reference to solvent medium and structure of thecomplex via ion pair charge transfer (IPCT) paves way for the novel reaction mechanism route. In thiswork, we prepared, characterized and photoinduced the complexes CoIII(pn)2(Cl)(L)2+ (where L =RC6H4NH2, R = m-OMe, p-F and H) in the presence of iodide ion. Quantum yield for 254 nm excitationof CoIII(pn)2(Cl)(L)2+(where L = RC6H4NH2, R = m-OMe, p-F and H) in water-1,4-dioxane mixtures(Diox = 0, 5, 10, 15, 20, 25, and 30% (v/v)) were also derived for all the complexes in presence ofadded iodide ion, in which CoIII was reduced via [CoIII(pn)2(Cl)(L)2+….. I-] ion-pair formation. Thephotoinduced state is ion-pair charge transfer transition state and the quantum efficiency is solventreliant and they are non-reactive. That is, change in ΦCo(II) is dependable with observed increase in xDioxof the mixed solvent medium. Correlation analysis using empirical parameters εr, Y, ETN and DNNprovides a model to understand the solvent medium participation and interaction. This work gains aninsight into the role of aqueous-organic solvent medium in CoIII(pn)2(Cl)(L)2+ photoreduction, whichmay be of great significance in developing novel approaches in the field of high performance catalysis