A new multifunctional di-topic tetrazolate-based ligand, 2,3-di-1H-tetrazol-5-ylpyrazine (H(2)dtp) has been designed and synthesized. The solvothermal reaction of this ligand with ZnCl(2) gave a robust guest-free three-dimensional zeolite-like chiral metal-organic framework (MOF) complex, [Zn(dtp)], which crystallized in chiral space group P6(1) and possessed chiral open channels with nitrogen-rich walls and the diameter of approximately 4.1 A. This framework presents a unique uniform etd (8,3) topology, is the first example of its type in MOFs, and exhibits high thermal stability with the decomposition temperature above 380 degrees C and permanent porosity. It is interesting that this material is able to selectively adsorb O(2) and CO(2) over N(2) gas, being a rare example in MOFs. In addition, C(2)H(2) and MeOH adsorption results show that although the framework channel holds nitrogen-rich walls that may provide H-bonding sites, no NH H-bond effect between the guest molecules and microporous surface was observed.

The in situ solvothermal reaction of 9,10-dicyanoanthracene and ZnCl(2)/NaN(3) gave the complex, {[Zn(7)(OH)(8)(DTA)(3)].H(2)O}(n) () (DTA(2-) = 9,10-ditetrazolateanthracene), which presents a pcu-type topological framework formed by DTA(2-) bridging unprecedented heptanuclear spindle [Zn(7)(OH)(8)](6+) clusters as SBUs, and exhibits strong luminescent emission with long lifetime.

An azido-metal-1,2,4-triazolate coordination polymer, [Cu(trz)(N(3))](n) (trz = 1,2,4-triazolate) was synthesized using hydrothermal methods; the complex has a rare three-dimensional non-interpenetrated utp or (10,3)-d topological network structure and exhibits spin-canted antiferromagnetism at low temperature.

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Seven new metal complexes with the formulas, [ Zn 2 (L 1 ) 2 (H 2 O)] n (1), [Cd 2 (L 1 )Cl 2 (H 2 O)] n (2), [Cd 3 (L 1 ) 3 (H 2 O) 12 ] and {[Cd 3 (L 3 ) 2 Cl 4 ] • (H 2 O) 4 } n (7), have been synthesized by the reactions of Zn II or Cd II salts with three structurally related flexible bis (tetrazol-5-yl) alkanes, 1,2-bis(tetrazol-5-yl)ethane (H 2 L 1 ), 1,3-bis(tetrazol-5-yl)propane (H 2 L 2 ), and 1,4-bis(tetrazol-5-yl)butane (H 2 L 3 ), and characterized by single crystal X-ray diffraction analysis, IR spectroscopy, and thermogravimetric (TG) analysis. Because of the geometrical requirements of different metal ions and the diverse coordination modes of the tetrazolate rings of flexible bis(tetrazole) ligands as well as the different reaction conditions, the obtained complexes show diverse structures from one-dimensional (1D) chain to three-dimensional (3D) coordination polymers. 1, 4, and 6 are Zn II complexes in which the Zn II ions show tetrahedral coordination geometries. 1 and 4 are 3D frameworks, while 6 is 1D chain structure. 2, 3, 5, and 7 are Cd II complexes, and the Cd II ions show octahedral coordination geometries. 3 is a twodimensional (2D) sheet and 2, 5, 7 are all 3D frameworks. The tetrazolate rings of the structurally related ligands adopt either µ 1 -tetrazolyl, µ 2 -tetrazolyl, µ 3 -tetrazolyl, or µ 4 -tetrazolyl modes in our obtained complexes. The fluorescent properties of these complexes have also been investigated in the solid state at room temperature.