Spectroscopic Studies of Charge-Transfer Complexation of Iodine with a New Benzo-Substituted Macrocyclic Diamide in Chloroform, Dichloromethane and H259heir 1:1 Mixture

Charge-transfer complexation of iodine with a new benzo-substituted macrocyclic diamide 5,6,7,8,9,10-hexahydro-2H-1,13,4,7,10-benzodioxatriazacyclopentadecine-3,11(4H,12H)-dione (L) with iodine was studied spectrophotometrically in chloroform, dichloromethane and their 1:1 (v/v) mixture. The observed time dependence of the charge-transfer band and subsequent formation of I3 - ion are related to the slow formation of the initially formed 1:1 L.I2 outer complex to an inner electron donor-acceptor (EDA) complex, followed by fast reaction of the inner complex with iodine to form a triiodide ion, as follows:L + I2 → L.I2 (outer complex), fast L.I2 (outer complex) → (L.I+)I- (inner complex), slow (L.I+)I- (inner complex) + I2 → (L.I+)I3 -, fast The pseudo-first-order rate constants for the transformation process were evaluated in different solvent systems. The stability constants of the resulting EDAr complexes were also evaluated and the solvent effect on their stability is discussed. The resultingcomplexes were isolated and characterized by FTIR and 1H NMR spectroscopy