Аннотация:Reactions of In(III)ClPc or Tl(III)ClPc phthalocyanines with monodeprotonated tetraphenylporphyrin HTPP(−) anions have been studied under reduction or in the presence of N-methylimidazole (N-MeIm). Formation of salt {In(III)(N-MeIm)2(TPP2−)}+{In(III)(Pc2−)2}(−)⋅ 4C6H4Cl2 (1) justifies partial abstraction of indium(III) atoms from In(III)ClPc to form cationic {In(III)(TPP(2−))}(+) porphyrins solvated byN-MeIm and double-decker {In(III)(Pc(2−))2}(−) anions. Crystals of Tl(I)(HTPP(−)) (2) have been only obtained at the interaction of HTPP(−) with Tl(III)ClPc under reduction indicating that Tl(III) is reduced to Tl(I) and is abstracted by HTPP(−). To confirm the possibility of Tl(I) formation under reduction we have studied reductionof Tl(III)ClPc by sodium fluorenone in the presence of cryptand[2.2.2]. Crystals of {Cryptand(Na+)}(Tl(I)(Pc(2−))}(−)⋅C6H4Cl2 (3) have been isolated indicating metal-centered reduction of Tl(III)ClPc to form Tl(I) and preserving dianionic Pc(2−) macrocycles. Optical spectra and structures of the obtained compounds are discussed and compared with those of pristine M(III)ClPc. It is shown that 1–3 are EPR silent due to the formation of diamagnetic components.