From iodoindium(III) phthalocyanine to the π-radical indium(III) diphthalocyanine and magnetically frustrated indium diacetate hydroxide coordination polymer

摘要

Two different compounds, the π-radical double-decker indium diphthalocyanine benzonitrile solvate (InPc2·2BN) and indium diacetate monohydroxide (In(OH)(CH_3COO)_2), have been obtained in a crystalline form from iodoindium phthalocyanine (InPcI). The first compound is monoclinic with centrosymmetric space group P2_1/m, while the second compound is orthorhombic with space group Cmcm. The indium cation in InPc_2·2BN is eight coordinated by N atoms of two phthalocyaninate rings, one of which is Pc(2-) and the other one is the π-radical one-electron oxidised Pc(1-). The unpaired electron has been identified by the EPR spectroscopy (g = 2.0025). The InPc _2·2BN compound was also characterised by UV-Vis spectroscopy. The second compound forms 1D coordination polymer of {In(OH)(CH _3COO)_2}_n bridged through the hydroxyl group and the acetate anions. In the 1D-polymeric chain the indium cation with slightly distorted octahedral geometry is coordinated in plane by four acetate ions having longer In-O bonds and two axial O atoms of hydroxyl groups with shorter In-O bonds. Additionally, the In(OH)(CH_3COO)_2 compound was characterised by IR spectroscopy. The magnetic measurements of In(OH)(CH _3COO)_2 point to the orientational frustration and below 2.5 K the compound exhibits transition to the superconducting phase.