The development of zeolite-like structures with extra-large pores (>12-membered rings, 12R) has been sporadic and is currently at 30R. In general, templating via molecules leads to crystalline frameworks, whereas the use of organized assemblies that permit much larger pores produces noncrystalline frameworks. Synthetic methods that generate crystallinity from both discrete templates and organized assemblies represent a viable design strategy for developing crystalline porous inorganic frameworks spanning the micro and meso regimes. We show that by integrating templating mechanisms for both zeolites and mesoporous silica in a single system, the channel size for gallium zincophosphites can be systematically tuned from 24R and 28R to 40R, 48R, 56R, 64R, and 72R. Although the materials have low thermal stability and retain their templating agents, single-activator doping of Mn(2+) can create white-light photoluminescence.

A novel vanadium(V) phosphate and the arsenate analogue, [(VO(2))(2)(4,4'-bpy)(0.5)(4,4'-Hbpy)(XO(4))].H(2)O (X = P, As; bpy = bipyridine), have been synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction. They are the first structurally characterized compounds in the vanadium(V)/4,4'-bpy/phosphate (or arsenate) systems. The two compounds are isostructural and crystallize in the triclinic space group P macro (No. 2) with a = 7.9063(3) A, b = 10.2201(4) A, c = 12.1336(5) A, alpha = 113.4652(7) degrees, beta = 95.7231(7) degrees, gamma = 94.4447(7) degrees, and Z = 2 for the phosphate, and a = 7.8843(6) A, b = 10.3686(7) A, c = 12.2606(9) A, alpha = 113.464(1) degrees, beta = 95.560(1) degrees, gamma = 94.585(1) degrees, and Z = 2 for the arsenate. The structure consists of phosphate-bridged vanadium(V) double chains linked through 4,4'-bpy ligands to form a sheet with the monoprotonated 4,4'-Hbpy(+) ligand being coordinated to the metal atom as a pendent group. The (1)H MAS NMR spectrum exhibits four resonances at 14.2, 9.5, 7.2, and 3.7 ppm with an intensity ratio close to 1:6:6:2, corresponding to three different types of protons in 4,4'-bpy and 4,4'-Hbpy(+) and one type of protons in H(2)O. The peak at 14.2 ppm can be assigned to the proton bonded to the pyridine nitrogen atom, which confirms the presence of 4,4'-Hbpy(+).

Two new hybrid polymeric iodoargentates, [Ag2I2(phen)] n (1; phen = 1,10-phenanthroline) and [AgI­(bpt)] n (2; bpt = 3,5-bis­(pyrazinyl)-1,2,4-triazole), were prepared by the hydrothermal methods. 1 displays a new type of taenioid, [Ag2I2(phen)] n , chain incorporating phen molecules, while 2 exhibits a unique 2D hybrid iodoargentate based on a combination of the [AgI] n layer and bpt molecules as electron acceptors. Such a 2D layer is the first example of an inorganic iodoargentate layer covalently bonding to aromatic N-heterocycle derivatives within the iodoargentates. 1 and 2 exhibit photocurrent response properties.

One novel three-dimensional (3-D) copper(I)-thioarsenate(III) [Ni(en) 3 ]Cu 4 As 4 S 9 (1, en = ethylenediamine) has been solvothermally prepared with the utilization of the in situ formation of [Ni(en) 3 ] 2+ complex as structure-directing agent (SDA). 1 contains cubane-like [Cu 8 S 12 ] 16− clusters and rare tetrameric [As 4 S 9 ] 6− units, which are interconnected to generate the first example of a 3-D anionic framework [Cu 4 As 4 S 9 ] n2n− , topologically identical to pyrite, and having large channels filled by [Ni(en) 3 ] 2+ complex cations. 1 is a potential wide-band-gap semiconductor with an energy gap of 1.91 eV that exhibits selectively photocatalytic degradation of methylene blue under visible-light irradiation. The density functional theory calculation, photocurrent response, and magnetic properties of 1 were also investigated.