Porous and Nanorod-Like Coordination Polymers Assembled from a New V-Shaped Bis(1,2,4-triazolyl)tripyridine Ligand

Six complexes based on a new rigid V-shaped ligand, 2,6-bis(3-(pyrid-4-yl)-1,2,4-triazolyl)pyridine (2,6-H 2 bptp), namely, [Cd 4 (2,6-bptp) 2 ( d -cam)( l -cam)(H 2 O) 2 ] n ·4 n H 2 O ( 1 ), [Cd 2 (2,6-Hbptp) 2 (Hbtc)] n ·4 n H 2 O ( 2 ), [Zn(2,6-bptp)(H 2 O)] n · n H 2 O ( 3 ), [(Mo 8 O 26 )Cu 2 (2,6-H 2 bptp) 2 ] n ( 4 ), [Co(2,6-H 2 bptp) 2 ][Mo 8 O 26 ] 0.5 ·5H 2 O ( 5 ), and [(PMo 12 O 40 )Ag(2,6-H 4 bptp)]·2H 2 O ( 6 ) ( d / l -H 2 cam = d / l -camphoric acid; H 3 btc = 1,3,5-benzenetricarboxylic acid), have been synthesized under hydrothermal conditions. Among these complexes, 2,6-H 2 bptp adopts seven types of coordination modes; all display a central tridentate chelating plane. Complex 1 possesses a 3D porous metal–organic framework that exhibits an intriguing sandwich-like motif. Complex 2 is a 1D nanorod-like coordination polymer with a square section of 1.11 × 1.06 nm 2 . Complex 3 exhibits a 1D zigzag chain structure, which is extended to a supramolecular double-chain by hydrogen bonding. In complex 4, polyoxometalate β-Mo 8 O 26 4– links Cu 2 (2,6-H 2 bptp) 2 4+ dimer to form a 1D linear chain polymer. Complex 5 displays a 3D supramolecular architecture with nanosized tunnels in which β-[Mo 8 O 26 ] 4– clusters embed. Complex 6 is a mononuclear silver complex constructed from Ag(2,6-H 4 bptp) 3+ and [PMo 12 O 40 ] 3– pieces, which is further extended to a 3D supramolecular framework. The metal–organic frameworks of 1 and 2 are thermally stable up to 440 °C. Both Cd(II) complexes emit blue luminescence originating from ligand-centered emission. Complex 4 shows weak antiferromagnetic coupling in the Cu 2 (2,6-H 2 bptp) 2 4+ dimer.