A gel aging effect in the synthesis of open-framework gallium phosphates: structure solution and solid-state NMR of a large-pore, open-framework material

The templated zeolite-analogue GaPO-34 (CHA structure type) crystallises from a gel precursor Ga₂O₃ : 2H₃PO₄ : 1HF : 1.7SDA : 70H2O (where SDA = structure directing agent), treated hydrothermally for 24 hours at 170 °C using either pyridine or 1-methylimizadole as SDA and one of either poorly crystalline ε-Ga₂O₃ or γ-Ga₂O₃ as gallium precursor. If the same gels are stirred for periods shorter than 2 hours but treated under identical hydrothermal conditions, then a second phase crystallises, free of GaPO-34. If β-Ga₂O₃ is used as a reagent only the second phase is found to crystallise, irrespective of gel aging time. The competing phase, which we denote GaPO-34A, has been structurally characterised using synchrotron powder X-ray diffraction for the pyridine material, GaPO-34A(pyr), and using single-crystal X-ray diffraction for the 1-methylimiazole material, GaPO-34A(mim). The structure of GaPO-34A(pyr), P[1 with combining macron], a = 10.22682(6) Å, b = 12.09585(7) Å, c = 13.86713(8) Å, α = 104.6531(4)°, β = 100.8111(6)°, γ = 102.5228(6)°, contains 7 unique gallium sites and 6 phosphorus sites, with empirical formula [Ga₇P₆O₂₄(OH)₂F₃(H₂O)₂]·2(C₅NH₆). GaPO-34A(mim) is isostructural but is modelled as a half volume unit cell, P[1 with combining macron], a = 5.0991(2) Å, b = 12.0631(6) Å, c = 13.8405(9) Å, α = 104.626(5)°, β = 100.346(5)°, γ = 101.936(4)°, with a gallium and a bridging fluoride partially occupied and two partially occupied SDA sites. Solid-state ³¹P and ⁷¹Ga NMR spectroscopy confirms the structural complexity of GaPO-34A with signals resulting from overlapping lineshapes from multiple Ga and P sites, while ¹H and ¹³C solid-state NMR spectra confirm the presence of the protonated SDA and provide evidence for disorder in the SDA. The protonated SDA is located in 14-ring one-dimensional channels with hydrogen bonding deduced from the SDA nitrogens to framework oxygen distances. Upon thermal treatment to investigate SDA removal, structure collapse occurs, which may be due the large number of bridging hydroxides and fluorides in the as-made material, and the unequal amounts of gallium and phosphorus present.