Title: Structure- and solvent-property relationships for the electronic energies of charge-transfer complexes between certain benzene derivatives
Abstract: A che mic al model is proposed for describing c harge-tran sfe r co mplexes be twee n aromatic amin es and e lec tron-acce pting be nze ne d e rivativ es c ontaining a group having a doubl e-or triple-bond conjugated with th e ben ze ne ring.Accordin g to thi s mod el, an e lectron migrate s from the nitroge n atom of the amin e to on e of th e atom s of the multipl e-bonded group durin g c harge-transfer inte rac tion .Struc ture-prope rty re lation s hips we re de rive d for correlatin g: (I ), th e tran siti on e ne rgies of th e complexes; (2), the ionization , or oxidation , pote ntia ls of th e amines, a nd (3), th e e lec tron affiniti es or reduc tion pote ntial s of th e e lec tron acce ptors, with th e e lectron•donating abiliti es of th e s ub s titue nts of th e various co mpound s.Trans iti on e ne rgies cal c ulate d from re porte d spec trosco pi c d ata for these complexes we re correlate d using equation s de rive d in thi s s tudy.Simila rly corre lated were re ported data for th e a bov e properti es of th e amin e and e lec tron acceptor.Equation s we re de rive d for correlating th e e ffect of variation in solve nt on th e tran sition en e rgies of th e co mplexes.Corre lation of re porte d s pec troscopi c data indicated that th e greates t effec t is cau sed by variation in th e refra c tiv e index; of seco ndary importance was the c hange in di e lec tri c cons tant.