Layered Structures Constructed from New Linkages of Ge₇(O,OH,F)₁₉ Clusters

Abstract

Three new germanate solids, ASU-19, ASU-20-DAPe, and ASU-20-DACH, have been synthesized under hydrothermal conditions using respectively 1,4-diaminobutane (DAB), 1,5-diaminopentane (DAPe), and 1,4-diaminocyclohexane (DACH) as bases. The structures of ASU-19 and ASU-20-DACH have been characterized by single-crystal X-ray diffraction: ASU-19, Ge 14 O 29 X 4 ‚[GeOX 2 ]‚[H 2 DAB] 3 ‚3.8H 2 O (X ) F or OH), space group P1 h, a ) 11.4191(5), b ) 12.0525(6), c ) 18.1847(8) Å, R ) 90.704(1)°, β ) 92.635(1)°, γ ) 91.389(1)°, V ) 2499.1(2) Å 3 ; ASU-20-DACH: Ge 7 O 14 X 3 ‚[H 2 DACH] 1.5 ‚2H 2 O, space group C2/c, a ) 15.9525(11), b ) 17.5476(12), c ) 19.0027(13) Å, β ) 109.446(1)°, and V ) 5015.9(6) Å 3 . The structure of ASU-20-DAPe, Ge 7 O 14 X 3 ‚[H 2 DAPe] 1.5 ‚H 2 O, has been determined from X-ray powder diffraction data: space group C2/c, a ) 16.3180(5), b ) 16.6125(4), c ) 17.8898(6) Å, β ) 99.684-(2)°, V ) 4780.5(3) Å 3 . All three structures are based on the assembly of the same cluster Ge 7 (O,OH,F) 19 . The two ASU-20 structures consist of a slab of four-connected clusters. In ASU-19, the same layers are connected pairwise through a GeO 2 X 2 spacer, generating a slab structure, with slab thickness ca. 20 Å. The existence of the same layer in the presence of three different organic bases shows the adaptability of the structures to molecules differing in size, shape, and symmetry.

Germanates of 1D Chains, 2D Layers, and 3D Frameworks Built from Ge–O Clusters by Using Metal‐Complex Templates: Host–Guest Symmetry and Chirality Transfer

“…Similar Ge 7 X 19 cluster units were observed in ASU‐12,8i ASU‐16,8c ASU‐19,8l ASU‐20,8l and Ge 10 O 21 (OH)⋅ N 4 C 6 H 21 8k by using different bases as templates. Seven of the anions in this cluster are singly coordinated and available for linkage when the clusters condense into a framework, but the presence of partly terminal anions can prevent the Ge 7 X 19 clusters from completely connecting, thus generating interrupted structures.…”

“…For 1 , the unknown [In(dien) 2 ] 3+ complex cations are self‐organized in the reaction medium and play the role of a cooperative template with the organic amine in the formation of the inorganic networks. When In 2 O 3 was removed from the reaction system, a new layered germanate, Ge 7 O 14 F 3 (H 2 dien) 1.5 ⋅H 2 O,36 with the ASU‐208l framework structure was isolated. FJ‐ 1 a /FJ‐ 1 b was initially obtained by using ethylene glycol as solvent in the presence of [NiL 3 ]Cl 2 ⋅2H 2 O (L=en, enMe) as template 35.…”

SU‐16: A Three‐Dimensional Open‐Framework Borogermanate with a Novel Zeolite Topology

“…In the presence of hydrofluoric acid, boron could not be incorporated into the framework. Instead, a layered germanate (SU-17) with the same framework structure as ASU-20 [16] was formed. We have shown for the first time that the two kinds of tetrahedra BO 4 and GeO 4 , which differ very much in size (TÀ O 1.48 and 1.74 , respectively), can be connected to form an open framework with three-dimensional intersecting 12-and 8-ring channels.…”

Germanate Frameworks Constructed from Oxo Germanium Cluster Building Units

“…[38] The most striking structural feature of germanates constructed from Ge 7 clusters is the presence of extra-large channels. As shown in Figure 3a, Ge 7 O 14.5 F 2 ·[(CH 3 ) 2 NH 2 ] 3 -(H 2 O) 0.86 (ASU-12) has a three-dimensional inorganic framework with 16-membered-ring channels delimited by six Ge 7 clusters.…”