The systematic exploration of the phase diagram of the GeO(2)-1,6-diaminohexane-water-pyridine-HF system has allowed the identification of specific roles of the HF, H(2)O contents, and HF/H(2)O ratio in the formation of Ge(7)X(19) (Ge(7)), Ge(9)X(25-26) (Ge(9)), and Ge(10)X(28) (Ge(10)) clusters (X = O, OH, F). This work has led to the discovery of two novel structures with extra-large 18-membered rings accommodating 1,6-diaminohexane (DAH): SU-63, |1.5H(2)DAH|[Ge(7)O(14)X(3)]·2H(2)O, a layered germanate constructed from Ge(7) clusters with the Kagomé topology, and SU-64, |11H(2)DAH|[Ge(9)O(18)X(4)][Ge(7)O(14)X(3)](6)·16H(2)O, a germanate built of two-dimensional slabs containing both Ge(7) and Ge(9) clusters (X = OH or F). We also put SU-64 in context with previously reported cluster germanate compounds with related topologies by means of a simple crystal deconstruction study.

We present a novel open-framework oxide material constructed from Ge(10)(O,OH)(28) (Ge(10)) oxide clusters prepared via a nonsurfactant route. The material shows two distinct pore windows of 9.43 and 4.65 A and a low framework density structure of 12.7 Ge atoms per 1000 A(3). The topological study leads to the recognition of a newly observed trinodal 6,7-heterocoordinated net related to the 7-coordinated swh net. The structure displays large rigid cylinders showing features indicating a growth mechanism by hard-sphere packing of the inorganic moiety similar to that observed in mesoporous materials.

A novel open-framework germanate, denoted as SU-74-MPMD, was prepared by hydrothermal synthesis using 2methylpentamethylenediamine (MPMD) as the organic structure directing agent (SDA). The structure of SU-74-MPMD was determined from synchrotron X-ray powder diffraction (XRPD) data using the charge-flipping algorithm, and is one of the most complicated germanates solved from X-ray powder diffraction. The structure is built of layers of Ge 10 O 26 (OH) 2 (Ge 10 ) clusters that are connected by additional GeO 4 tetrahedra to form a threedimensional (3D) framework with 10-and 12-rings. The organic structure directing agent MPMD in the pores was located by simulated annealing. SU-74-MPMD: space group P2 1 /c, a = 12.62726(4) Å, b = 17.35186 (5) Å, c = 16.17343(5) Å, β = 115.5509(2)°and Z = 4. SU-74 was later synthesized using 1-(2aminoethyl)piperazine (AEP) as the SDA (denoted as SU-74-AEP), and its structure was solved by single crystal synchrotron Xray diffraction. The framework structure of SU-74-AEP is the same as that of SU-74-MPMD. The locations of the organic SDAs in the pores are different for SU-74-MPMD and SU-74-AEP, suggesting a space-filling role of the SDAs. The Ge 10 clusters follow the fcu-11-P2 1 /c net. The underlying topology of SU-74 is compared to those of other Ge 10 structures containing additional GeO 4 tetrahedra. The presence of additional tetrahedra can significantly affect the framework topology through the addition of edges between the Ge 10 nodes.

Three new bismuth arylsulfonatocarboxylates [Bi(OH)(SB)] (

Vanillic acid, C 8 H 8 O 4 , is a possible product from a future biorefinery with lignin as raw material. Two coordination compounds with this ligand in two different protonation states were prepared: 1 [Zn(C 8 H 7 O 4 ) 2 (H 2 O) 2 ] and 2 [Co 2 (C 8 H 6 O 4 ) 2 (H 2 O) 6 ] · 2H 2 O. Both compounds form extended 3Dstructures with strong hydrogen bonds. A high symmetry 8and 4-connected network topology, jus, is found in 1. The dinuclear coordination entity in 2 hints at a potentially useful SBU for MOF synthesis from lignin based bridging ligands.