(Phthalocyaninato)iron(II), Fe(pc), was oxidized in a solution of iodine in hot 1-chloronaphthalene. Two products were isolated: [FeCl(pc)]2I2, which is a new compound formed by reaction with the solvent, and the molecular conductor Fe(pc)I. [FeCl(pc)]2I2 crystallizes in space group C1i-P1 of the triclinic system with 1 formula unit in a cell of dimensions a = 12.270 (7) Å, b = 13.202 (7) Å, c = 8.335 (6) Å, a = 92.80 (3)°, β = 97.17 (3)°, and γ = 101.97 (2)° at 113 K. Full-matrix least-squares refinement of 388 variables gives a final value for R (on F02) of 0.066 for 6847 observations. The structure consists of two square-pyramidal FeCl(pc) units linked by I2 via the axial chloro ligands. The four halogens form an essentially linear unit. The 57Fe Mössbauer spectrum is consistent with this structure. Fe(pc)I crystallizes in space group D4h2-P4/mcc of the tetragonal system with 2 formula units in a cell of dimensions a = 13.84 (2) Å and c = 6.77 (1) Å at 97 K. Full-matrix least-squares refinement of 35 variables gives a final value of 0.177 for the R index (on F02) for 620 observations. The structure consists of chains of Fe(pc) molecules, stacked metal over metal. Adjacent Fe(pc) molecules in the unit cell are staggered by 40°. Disordered chains of I3- lie in channels between the Fe(pc) stacks. The iodine is identified as I3- by resonance Raman spectroscopy. The single-crystal conductivity of Fe(pc)I is 20 Ω-1 cm-1 at 20 °C; the conductivity increases with decreasing temperature.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry