Exceptionally Stable, Hollow Tubular Metal−Organic Architectures:  Synthesis, Characterization, and Solid-State Transformation Study

Abstract

An effective solvothermal procedure has been developed to synthesize the new three-dimensional metal-organic framework, [ZnF(AmTAZ)].solvents, using either 3-amino-1,2,4-triazole (AmTAZ) or 3-amino-1,2,4-triazole-5-carboxylic acid (AmTAZAc) and a choice of several Zn(II) salts as starting materials. The three-dimensional structure displays open-ended, hollow nanotubular channels that are formed by hexanuclear metallamacrocyclic Zn(6)F(6)(AmTAZ)(6) rings. The framework integrity is maintained to 350 degrees C, at which point most of the guest solvent molecules have been removed, as evidenced by single-crystal X-ray analyses, (1)H solid-state NMR, and TGA measurements. At higher temperatures, the framework is converted either to zinc oxide (ZnO) when heated in air or to zinc cyanamide (ZnCN(2)) when heated in an inert atmosphere. In both cases, the as-grown, rodlike crystal shape is maintained during the solid-state transformation, suggesting a possible route for preparing one-dimensional crystalline nanomaterials.

Topological ferrimagnetism and superparamagnetic-like behaviour in a disordered homometallic coordination network

“…We note that in principle diffuse scattering studies should qualify our model and could quantify the extent of any disorder. Although local orientational disorder of this ligand has been reported previously, [9] in this case stereo-kinetic considerations suggest that once a particular orientation for a Co II tetrahedron occurs, then that orientation is propagated along the stack as the crystal grows. This type of disorder allows the entire structure to be divided into structurally ordered domains.…”

Synthesis, X-ray crystal structure, thermal and solution studies of a centrosymmetric metal–organic polymer based on proton transfer methodology

“…A variety of factors can influence the self-assembly of coordination frameworks making desired topologies and specific properties a difficult challenge [1][2][3][4][5]. Construction of coordination polymers with new network motifs is of interest for the development of new functional materials and in the fundamental studies of crystal engineering and supramolecular chemistry [6][7][8][9][10][11][12][13].…”

Orthogonality of Jahn–Teller axes in a dinuclear Cu(ii) complex bridged by one F− anion

“…6 The bridged F -anion originates from the hydrolysis of one equivalent of the BF 4 -anion, 7 a well-documented phenomenon that has also been utilized to yield coordination compounds with bridged F -anions. 8,9 Fig. 1 ORTEP drawing of 1 (thermal ellipsoids drawn at 50% probability).…”