Self‐Assembly of Silver(I) Coordination Polymers from AgX (X = BF₄^–, ClO₄^–, CF₃COO^–, and SO₃CF₃^–) and a Rigid Bent 3,6‐Dicyano‐9‐phenylcarbazole Ligand: The Templating Effect of Anions

Abstract

Abstract One rigid bent bridging ligand with highly planar π‐conjugated spacers, 3,6‐dicyano‐9‐phenylcarbazole (dcphcz), was designed and synthesized. The coordination reactions of dcphcz with a series of Ag I salts with different counterions has been investigated. Four coordination polymers were obtained by solution reactions and characterized by IR,elemental analysis, and single‐crystal X‐ray diffraction. The solid‐state structures of {[Ag(dcphcz)]BF 4 } n ( 1 ) and {[Ag(dcphcz)]ClO 4 } n ( 2 ), exhibit similar 1D “zigzag” patterns. The complex {[Ag(dcphcz)][Ag 2 (dcphcz)(H 2 O) 2 ](SO 3 CF 3 ) 3 · C 6 H 6 · (H 2 O) 2 } n ( 3 ) includes two different one‐dimensional (1D) chain units: one forms double‐layer two‐dimensional (2D) metal–organic frameworks (MOFs) through intermolecular Ag–O–Ag bridging interactions, the other features double‐layer 2D supramolecular networks through C–H ··· O hydrogen‐bonding interactions. The complex [Ag 2 (dcphcz)(CF 3 COO) 2 ] n ( 4 ) features a bundle of novel nanotubular structures, which contain silver chains formed by carboxylate spacers. Furthermore, all these complexes are connected by face‐to‐face π ··· π stacking interactions between carbazolyl planes, affording a series of three‐dimensional (3D) architectures with different structural geometries. The structuraldiversities of these complexes demonstrated that counteranions and bridging ligands play essential roles in the construction of supramolecular frameworks. In addition, the luminescence properties of the free ligand dcphcz and complexes 1 – 4 were investigated.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)