Self-Assemblies of New Rigid Angular Ligands and Metal Centers toward the Rational Construction and Modification of Novel Coordination Polymer Networks

Self-assemblies of rigid angular ligands with 120° molecular angle and metal centers have been investigated with the aim of achieving the rational construction and modification of coordination polymer structures. The reactions of Co(NCS)2 with 1,3-bis(trans-4-styrylpyridyl)benzene (L 1 ), 2,6-bis(trans-4-styrylpyridyl)pyridine (L 2 ), 1,3-bis(trans-4-styrylpyrimidyl)benzene (L 3 ), and 1,3-bis(trans-4-styrylquinoly)benzene (L 4 ) afford complexes [Co(L 1 )2(NCS)2]∞ (1), [Co(L 2 )2(NCS)2]∞ (2), Co(L 3 )2(NCS)2(CH3OH)2 (3), and [Co(L 4 )(NCS)2]∞ (4), respectively. The resulting complexes exhibit open framework, stairlike hydrogen-bonded chain and single-stranded helical coil structures, which are controlled by the variation of the geometry around the coordination site in ligands. Moreover, the coordination of L 1 and L 2 to Mn(hfac)2 (hfac = 1,1,1,5,5,5-hexafluoroacetylacetonate) yields single-stranded helical coordination polymers of [Mn(L 1 )(hfac)2]∞ (5) and [Mn(L 2 )(hfac)2]∞ (6), respectively.