首页|Salts of vanadyl phthalocyanine {V~(IV)O(Pc~(·3-))}~-anions with decamethylmetallocenium cations(Cp*2M~+,M = Cr~(III)and Co~(III)).Ferromagnetic coupling in the [(Cp*2Cr~+){V~(IV)O(Pc~(·3-))}~-]2 assemblies
Salts of vanadyl phthalocyanine {V~(IV)O(Pc~(·3-))}~-anions with decamethylmetallocenium cations(Cp*2M~+,M = Cr~(III)and Co~(III)).Ferromagnetic coupling in the [(Cp*2Cr~+){V~(IV)O(Pc~(·3-))}~-]2 assemblies
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Vanadyl phthalocyanine {V~(IV)O(Pc~(2-))}~0 was reduced by decamethylchromocene or decamethylcobaltocene(Cp*2M~(II)),and the crystals of the complexes were precipitated by n-hexane.Reduction of this phthalocyanine is centered on the macrocycle providing the formation of the {V~(IV)O(Pc~(·3-))}-anions containing two paramagnetic V~(IV)and Pc~(·3-)centers with an S = 1/2 spin state.These paramagnetic anions coexist in(Cp*2Cr+){VIvO(Pc~(·3-))}~-3C6H4Cl2(1)with the high-spin(S = 3/2)Cp*2Cr~+ counter cations.Nearly isolated assemblies in which two Cp*2Cr~+ cations are sandwiched between two {V~(IV)O(Pc~(·3-))}~-anions are formed in 1.Effective magnetic moment of 1 of 4.57 μB at 300 K corresponds to the contribution of noninteracting V~(IV),Pc~(·3-)and Gr~(III)spins.Weiss temperature of +4 K indicates weak ferromagnetic coupling of spins.Effective magnetic moment of 1 increases upon cooling up to 4.78 μB at 8 K and then drastically falls down.Such magnetic behavior is described well by ferromagnetic coupling between the V~(IV)and Pc~(·3-)spins with J1 = + 4.75 cm~(-1)and weaker ferro-magnetic interactions between Pc~(·3-)and Cr~(III)spins through the Cp* ligand with J2 = +1.08 cm~(-1).Weak anti-ferromagnetic coupling with J3 =-0.76 cm~(-1)is also present between the Cr~(III)spins.Complexes(Cp*2Co~+){V~(IV)O(Pc~(·3-))}~-·1.5C6H4C12(2)and(Cp*2Co~+){V~(IV)O(Pc~(·3-))}~-·C6H4Cl2(3)with the diamagnetic Cp*2Co~+ counter cations(S = 0)were also obtained allowing to study their crystal structures and optical properties.
PhthalocyanineReductionMagnetic assembliesCrystal structureOptical and magnetic properties
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