Abstract
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]TiIV(PcCl84-)}2- (1), (PPN+){O[double bond, length as m-dash]TiIV(Nc˙3-)}˙-·2C6H4Cl2 (2) and (PPN+)2{O[double bond, length as m-dash]TiIV(AceTPrzPz4-)}2-·1.3C6H4Cl2·0.8C6H5CN (3) where PPN+ is the bis(triphenylphosphoranylidene)ammonium cation, PcCl8 - 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]TiIV(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]TiIV(Pc˙3-)}˙- (995-998 nm). Reduction of macrocycles leads also to the alternation of C-Nimine 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]TiIV(PcCl84-)}2- and {O[double bond, length as m-dash]TiIV(AceTPrzPz4-)}2- dianions, respectively. Salt 2 contains nearly isolated [{O[double bond, length as m-dash]TiIV(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.
Highlights
Metal phthalocyanine compounds possess promising optical, conducting and magnetic properties
Crystalline anionic salts of titanyl macrocycles with acceptor substituents or an extended π-system have been obtained for the first time: (PPN+)2{OvTiIV(PcCl84−)}2− (1), (PPN+){OvTiIV(Nc3−)}−·2C6H4Cl2 (2) and (PPN+)2{OvTiIV(AceTPrzPz4−)}2−·1.3C6H4Cl2·0.8C6H5CN (3) where PPN+ is the bis(triphenylphosphoranylidene)ammonium cation, PcCl8 – 2,3,9,10,16,17,23,24-octachlorophthalocyanine; Nc – 2,3naphthalocyanine, AceTPrzPz – tetra(acenaphthenopyrazino)porphyrazine
A series of radical anion and dianion salts based on titanyl macrocycles with acceptor substituents or an extended π-system were obtained as single crystals for the first time
Summary
Metal phthalocyanine compounds possess promising optical, conducting and magnetic properties. Radical anion and dianion salts of titanyl macrocycles with acceptor substituents or an extended π-system†
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