Hydrothermal synthesis and characterization of two new microporous zinc-substituted gallium phosphates templated by diaminocyclohexane: (H(2)DACH)(2)[Zn4Ga2(HPO4)(3)(PO4)(4)] and (H(2)DACH)[Zn2Ga2(PO4)(4)]

Two new zinc-substituted gallophosphates, (H(2)DACH)(2) [Zn4Ga2(HPO4)(3)(PO 4)(4)] (1) and (H(2)DACH) [Zn2Ga2(PO4)(4)] (2), have been synthesized under mild hydrothermal conditions and characterized by single-crystal X-ray dif fraction, solid-state NMR spectroscopy, and thermogravimetric analysis. Bot h structures are built up with MO4 (M = Zn, Ga) and PO4 (or HPO4) tetrahedr a. Compound 1 adopts a novel microporous framework which contains the highe st transition-metal concentration of any MGaPO. The structure may be viewed as stacking of [Zn2Ga(HPO4)(2)(PO4)(2)](2) layers along a linked by extra HPO4 tetrahedra as pillars to generate intersecting 12-ring channels with d imensions similar to8.1 x 8.1 Angstrom. Compound 2 has a CGS framework topo logy but a higher divalent-metal content than the isostructural materials o f (C7NH14)[MGa3P4O12] (M = CO, Zn). Diprotonated 1,2-diaminocyclohexane (DA CH) cations are ordered at the intersections of two interconnected channels in both 1 and 2. They represent the first zinc-substituted gallophosphate templated by dibasic amine and showing distinguishable Zn sites. The solid- state (31)p MAS NMR spectrum of 1 showed a resonance for the HPO42- group t hat was shifted downfield by similar to8 ppm relative to the PO43- group. O n the basis of the results of TG/DT analyses, both frameworks can be therma lly stable up to similar to 300 degreesC. Crystal data: 1, monoclinic, C2/c , a = 23.568(1) Angstrom, b = 10.242(1) Angstrom, 16.235(1) Angstrom, beta = 108.115(1)degrees, Z = 4; 2, monoclinic, P2(1)/c, a = 14.320(1) Angstrom, b 16.255(1) Angstrom, c = 8.855(1)Angstrom, beta = 90.134(1)4 Z = 4.