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-H2bptp), namely, [Cd4(2,6-bptp)2(d-cam)­(l-cam)­(H2O)2]n·4nH2O (1), [Cd2(2,6-Hbptp)2(Hbtc)]n·4nH2O (2), [Zn­(2,6-bptp)­(H2O)]n·nH2O (3), [(Mo8O26)­Cu2(2,6-H2bptp)2]n (4), [Co­(2,6-H2bptp)2]­[Mo8O26]0.5·5H2O (5), and [(PMo12O40)­Ag­(2,6-H4bptp)]·2H2O (6) (d/l-H2cam = d/l-camphoric acid; H3btc = 1,3,5-benzenetricarboxylic acid), have been synthesized under
hydrothermal conditions. Among these complexes, 2,6-H2bptp
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 nm2. Complex 3 exhibits a 1D zigzag chain structure, which is extended to a supramolecular
double-chain by hydrogen bonding. In complex 4, polyoxometalate
β-Mo8O264– links Cu2(2,6-H2bptp)24+ dimer to
form a 1D linear chain polymer. Complex 5 displays a
3D supramolecular architecture with nanosized tunnels in which β-[Mo8O26]4– clusters embed. Complex 6 is a mononuclear silver complex constructed from Ag­(2,6-H4bptp)3+ and [PMo12O40]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
Cu2(2,6-H2bptp)24+ dimer.