Intense near- and mid-infrared absorbing films of electrochemically crosslinked multinuclear metallodithiolene complex polymers

Abstract

Novel multinuclear metallodithiolene complexes [(Cbz) 2 -BTT-Pd(dppf)] 2 Ni[6b, Cbz=carbazole, BTT= benzene-1,2,4,5-tetrathiotate, dppf=1,1'-bis(diphenylphosphino) ferrocene] and polymer [(Cbz) 2 -BTT-Ni] n · [(Et) 3 (PhCH 2 )N] x (7b) with the carbazole pendent groups were synthesized and characterized. The thin films of crosslinked polymers P6b and P7b were prepared by electrochemical polymerization of compounds 6b and 7b, respectively. These films show intense and broad absorption in the near-and mid-infrared spectral regions(P6b: 1000-1600 nm, λ max =1297 nm; P7b: 800 nm-8 μm, λ max =3.9 μm) and are potentially useful as infrared optical materials.

Thiosemiquinoid Radical-Bridged CrIII2 Complexes with Strong Magnetic Exchange Coupling

“…While numerous studies of transition-metal complexes containing 1,2,4,5-tetrathiobenzene-based bridging ligands with Fe, Ni II , Pt II , , Rh III , Ir III , Ti IV , Zr IV , Hf IV , and Ru II have been reported, to our knowledge, a radical form of this ligand has been isolated only once, in a Ni II 2 complex . Moreover, a benzene tetrathiolate radical has not yet been investigated in the presence of paramagnetic metal centers nor has the magnetic exchange coupling been determined.…”