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Crystalline anionic salts of titanyl macrocycles with acceptor substituents or an extended π-system have been obtained for the first time: (PPN + ) 2 {O[double bond, length as m-dash]Ti IV (PcCl 8  4- )} 2- (1), (PPN + ){O[double bond, length as m-dash]Ti IV (Nc˙ 3- )}˙ - ·2C 6 H 4 Cl 2 (2) and (PPN + ) 2 {O[double bond, length as m-dash]Ti IV (AceTPrzPz 4- )} 2- ·1.3C 6 H 4 Cl 2 ·0.8C 6 H 5 CN (3) where PPN + is the bis(triphenylphosphoranylidene)ammonium cation, PcCl 8 - 2,3,9,10,16,17,23,24-octachlorophthalocyanine; Nc - 2,3-naphthalocyanine, AceTPrzPz - tetra(acenaphthenopyrazino)porphyrazine. Salts 1-3 were obtained in the reduction of the parent titanyl macrocycles by fluorenone ketyl in the presence of an excess of PPNCl in o-dichlorobenzene with following precipitation of crystals with n-hexane. Reduction of macrocycles in 1-3 is accompanied by the appearance of intense NIR bands in the solid spectra at 963-1159 nm. It has been found that the extended π-system with linear annulation in {O[double bond, length as m-dash]Ti IV (Nc˙ 3- )}˙ - provides the shift of the NIR band to smaller energies (1159 nm) in comparison with those in the spectra of {O[double bond, length as m-dash]Ti IV (Pc˙ 3- )}˙ - (995-998 nm). Reduction of macrocycles leads also to the alternation of C-N imine bonds due to partial disruption of their aromaticity. The disruption is higher for the dianions in 1 and 3 in comparison with the radical anions in 2. One-dimensional π-π stacking chains and layers are formed in 1 and 3 with diamagnetic {O[double bond, length as m-dash]Ti IV (PcCl 8  4- )} 2- and {O[double bond, length as m-dash]Ti IV (AceTPrzPz 4- )} 2- dianions, respectively. Salt 2 contains nearly isolated [{O[double bond, length as m-dash]Ti IV (Nc˙ 3- )}˙ - ] 2 dimers with a strong π-π interaction between paramagnetic radical anion macrocycles. As a result, a transition from the triplet to singlet state with antiparallel ordering of spins within the dimers is observed in 2 below 200 K.

Radical anion and dianion salts of titanyl macrocycles with acceptor substituents or an extended π-system