Coordination Networks from [Te₄]²⁺ Clusters and Polynitriles

Abstract The reactions of a series of organic polynitriles with [Te 4 ][AsF 6 ] 2 in liquid SO 2 solution lead either to reduction of [Te 4 ] 2+ to elemental tellurium or to the formation of coordination polymers. With 1,3‐dicyanobenzene (1,3‐DCB), 1,4‐dicyanobenzene (1,4‐DCB), 1,2,4,5‐tetracyanobenzene (TCB), tetracyanoethylene (TCNE) and tetracyanochinodimethane (TCNQ) the coordination complexes [Te 4 ][AsF 6 ] 2 ⋅ 2(1,3‐DCB), [Te 4 ][AsF 6 ] 2 ⋅ 3(1,4‐DCB) ⋅ 2SO 2 , [Te 4 ][AsF 6 ] 2 ⋅ TCB, [Te 4 ][AsF 6 ] 2 ⋅ TCNE and [Te 4 ][AsF 6 ] 2 ⋅ TCNQ ⋅ 8 SO 2 were isolated and characterized by crystal structure analyses and vibrational Raman spectroscopy. The nitriles are coordinated to the square‐planar clusters forming 1D chains, 2D arrangements and 3D networks. Tetrakis(dicyanomethylene)cyclobutendiide [C 4 (C{CN} 2 ) 4 ] 2− is oxidized by [Te 4 ] 2+ to the neutral cyanocarbon C 4 (C{CN} 2 ) 4 , structurally representing a 4[radialene]. The ionization potentials and electron affinities of the cyanamide anion, cyanogen, 1,2‐DCB, 1,3‐DCB, 1,4‐DCB, TCB, C 4 (C{CN} 2 ) 4 , TCNE and TCNQ and those polynitriles, which cause reduction of [Te 4 ] 2+ , were calculated at coupled‐cluster level of theory in order to examine possible reasons for the stability of the coordination polymers based on electronic properties of the nitriles.