화학공학소재연구정보센터
Inorganic Chemistry, Vol.46, No.25, 10840-10849, 2007
Effect of axial ligands and macrocyclic structure on redox potentials and electron-transfer mechanisms of Sn(IV) porphyrins
The electrochemical properties of dichloro- and dihydroxo-Sn(IV) porphyrins with three different macrocycles were examined in CH2Cl2 containing 0.1 or 0.2 M tetra-n-butylammonium perchlorate as supporting electrolyte. The investigated compounds are represented as (TPP)SnX2, (P)Sn(X)(2), and (PQ)Sn(X)(2), where TPP = 5,10,15,20-tetraphenylporphyrin, P = 5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)porphyrin, PO = 5,10,15,20-tetrakis(3,5-di-tert-butylphenyl)quinoxalino[2,3-b']porphyrin , and X = Cl or OH. Each porphyrin can be electroreduced in two one-electron-transfer steps with the half-wave potentials and stability of the eletroreduced compounds being dependent upon the type of coordinated axial ligand and specific macrocyclic structure. All reductions of (TPP)Sn(OH)(2), (P)Sn(OH)(2), and (PQ)Sn(OH)(2) are reversible under the given experimental conditions and lead to the expected porphyrin pi-anion radicals and dianions, which were characterized by thin-layer UV-vis spectroelectrochemistry. This contrasts with what occurs upon the reduction of (PQ)SnCl2, which undergoes a chemical reaction with trace H2O in solution, leading to the formation of (PQ)Sn(OH)(2) as well as to a protonated form of the quinoxalinoporphyrin, (PQH)Sn(OH)(2), under the application of an applied potential. A protonation of the Q group breaks the conjugation between the fused quinoxaline unit and the porphyrin macrocycle, thus effectively giving a compound whose reduction properties resemble that of the metalloporphyrin in the absence of the fused ring. The electrooxidation of each neutral Sn(IV) porphyrin was also investigated, and the effect of axial ligand and fused quinoxaline ring on the redox potentials and products of electron transfer are discussed.