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Ring oxidized green Cerium(IV)diphthalocyanines, [Ce(Pc) 2 ]X (X = (poly)halide, NO 3  - ) are prepared by chemical oxidation of ( n Bu 4 N)[Ce(Pc 2- ) 2 ] with the corresponding halogen in solution or of solid [Ce(Pc 2- ) 2 ] with aqueous HNO 3  Electrochemical oxidation of (nBu 4 N)[Ce(Pc 2- ) 2 ] in solution in the presence of ( n Bu 4 N)BF 4  yields [Ce(Pc) 2 ](BF 4 ) 0.33 , which crystallizes in the tetragonal space group P4/nnc (a, b = 19.643(3) Å, c = 6.525(3) A, Z = 2). The Ce IV  ion is eightfold coordinated by the isoindole N atoms (N iso ) of the two staggered (ca. 41°), slightly distorted Pc ligands. The “[Ce(Pc) 2 ] 0.33+ ” subunits are arranged in infinite columns along [001] with the Ce atoms statistically disordered over two positions and Ce - N iso  bond lengths of 2.45(1) and 2.69(1) A, respectively The UV-VIS spectrum is dominated by the transitions of the Pc 2-  ligand at ca. 15,000 (B band), 30,000 and 36,000 cm  -1  (Q, N region). A low energy (“metallic”) band at ca. 2800 cm  -1  typical for partially oxidized systems is present. The UV-VIS-NIR spectrum of [Ce(Pc) 2 ]NO 3  indicates a cofacial Pc 2-  - P c -  complex. In addition to the π-π’ transitions of the Pc 2-  moiety at ca. 14,000, 30,000 and 36,000 cm -1 , the Ch transition of the Pc- ring is observed at ca. 19,200 cm  -1  and the typical NIR band at 6380 cm  -1 . Oxidation of a thin film of (PNP)[Ce(Pc 2- )2] with dry Br 2 / N 2  gas yields purple [Ce(Pc - ) 2 ]Br x , whose UV-VIS-NIR spectrum shows the diagnostic features of dimeric Pc -  radicals with intense bands at ca. 14,000 and 18,000 cm  -1  assigned as B and Q 1  bands, respectively. At ca. 9000 cm -1  the typical Q D  absorption is observed. The vibrational spectra are dominated by the transitions of the Pc -  ligand at 1305/1445 cm  -1  (IR) and 560/1120/1172/1591 cm -1  (resonance Raman). Excitation with 1064 nm strongly enhances the sym. C e-N stretch at 163 c m  -1 .

Syntheses and Properties of Cerium Diphthalocyanines in High Oxidation States; Crystal Structure of [Ce(Pc) 2 ](BF 4 ) 0.33