Synthesis, spectral characterisation and crystal structure of (1,24-bicyclophthalocyaninato)bismuth(III)

A. new orange bicyclophthalocyanine complex of bismuth(III), [Bi(C48H24N13) ], has been synthesised by means of the template reaction of bismuth(III) a cetate with phthalodinitrile. The ligand consists of the phthalocyanine ske leton, which is bridged by two additional isoindole units. The conjugation of the phthalocyanine ring is interrupted by the two bridgehead sp(3)-hybri dised carbon atoms. The main difference between this new bicyclophthalocyan ine and those previously reported in the Literature lies in the position of the bridgehead carbon atoms. In order to differentiate between these bicyc lophthalocyaninato complexes, we propose a nomenclature: [Bi(C48H24N13)] is named Bi(1,24-Pcc), and the other bicyclic ligands already reported in the literature are named (1,16-Pcc) and (1,17-Pcc). The molecular structure of Bi(1,24-Pcc) shows the coordination polyhedron around the bismuth atom, ma de up of the six isoindole nitrogen atoms of the macrocycle, as a strongly distorted trigonal prism. The two Bi-N-iso bonds of the bridge and two of t he four Bi-N-iso bonds of the (Pc) ring have bond lengths between 2.40 and 2.47 Angstrom. One of the remaining bonds is longer (2.55 Angstrom), and th e sixth has a very short length of 2.20 Angstrom. This new complex was full y characterised by UV/Vis and IR spectroscopy, also reported here.