Interaction of InIIIClPc and TlIIIClPc phthalocyanines with deprotonated porphyrin HTPP− anions. Metal-centred reduction of TlIIIClPc

Abstract

Reactions of InIIIClPc or TlIIIClPc phthalocyanines with monodeprotonated tetraphenylporphyrin HTPP[Formula: see text] anions have been studied under reduction or in the presence of [Formula: see text]-methylimidazole ([Formula: see text]-MeIm). Formation of salt {InIII[Formula: see text]-MeIm)2(TPP[Formula: see text]}[Formula: see text]{InIII(Pc[Formula: see text]}[Formula: see text]⋅4C6H4Cl2 (1) justifies partial abstraction of indium(III) atoms from InIIIClPc to form cationic {InIII(TPP[Formula: see text]}[Formula: see text] porphyrins[Formula: see text]solvated by [Formula: see text]-MeIm and double-decker {InIII(Pc[Formula: see text]}[Formula: see text] anions. Crystals of TlI(HTPP[Formula: see text] (2) have been only obtained at the interaction of HTPP[Formula: see text] with TlIIIClPc under reduction indicating that TlIII is reduced to TlI and is abstracted by HTPP[Formula: see text]. To confirm the possibility of TlI formation under reduction we have studied reduction of TlIIIClPc by sodium fluorenone in the presence of cryptand[2.2.2]. Crystals of {Cryptand(Na[Formula: see text]}(TlI(Pc[Formula: see text]}[Formula: see text]⋅C6H4Cl[Formula: see text] (3) have been isolated indicating metal-centered reduction of TlIIIClPc to form TlI and preserving dianionic Pc[Formula: see text] macrocycles. Optical spectra and structures of the obtained compounds are discussed and compared with those of pristine MIIIClPc. It is shown that 1– 3 are EPR silent due to the formation of diamagnetic components.