Nickel Thiazoledithiolenes: π-Extended Fused-Ring Metal Dithiolenes as Highly Delocalized π-Electron Systems with...

Building off previous work on π-extended nickel thiophenedithiolenes, a series of thiazole-fused nickel dithiolene complexes have been prepared via similar synthetic methods, thus allowing for the addition of aryl groups to the terminal α-position of the fused thiazoledithiolene unit. In addition to π-extended complexes incorporating thiophene, phenyl, and furan end-groups, the methyl-terminated species has also been prepared as a representative of the simple nickel thiazoledithiolene core. The optical, electronic, and structural properties of these complexes have been characterized, and comparisons to the analogous nickel thiophenedithiolenes show that the replacement of thiophene by thiazole stabilizes the frontier orbitals of the thiazole-based complexes, while preserving the planar geometry, electronic delocalization, and low-energy NIR absorption of the previous nickel thiophenedithiolene species.