Coordination complexes with the redox active tetrathiafulvalene based imino-pyrazine ligand: syntheses, a radical cation salt, crystal structures and electrochemistry.
Abstract
The tetrathiafulvalene based 2-imino-pyrazine deriv. (TTF-CHN-2-pyz) (I) was synthesized and characterized. Its radical cation salt (I·+PF6-) was prepd. as single crystals by electrocrystn. I·+PF6- crystallizes in the triclinic P̅1 space group. Four 1:2 M(hfac)2 (Hhfac = hexafluoroacetylacetone) complexes coordinated with I were prepd. (M = Mn for 2, M = Co for 3, M = Cu for 4 and M = Zn for 5). Complex 2 crystallizes in the monoclinic C2/c space group, complexes 4 and 5 crystallize in the triclinic space group P̅1. Two pyrazine N atoms from two different donors are coordinated in cis configuration for 2 and trans configuration for 4 and 5 to the metallic ion of M(hfac)2. The Mn atom adopts a pseudo-compressed octahedral geometry while the Cu and the Zn ions adopt axially elongated octahedral geometries. Both crystal packing structures and electrochem. properties are appropriate for their potential use as starting mol. bricks for conducting and magnetic materials.
Keywords
crystal structure transition metal fluoroacetylacetonate tetrathiafulvalene imino pyrazine complex
electronic structure tetrathiafulvalene imino pyrazine radical cation
electrooxidn tetrathiafulvalene imino pyrazine transition metal complex
electroredn tetrathiafulvalene imino pyrazine transition metal complex
tetrathiafulvalene imino pyrazine prepn structure complexation transition metal
transition metal fluoroacetylacetonate tetrathiafulvalene imino pyrazine complex prepn