Thixotropic hydrogel derived from a product of an organic solid-state synthesis: Properties and densities of metal-organic nanoparticles

Abstract

Metallogels form from Cu(II) ions and tetratopic ligand rctt-1,2-bis(3-pyridyl)-3,4-bis(4-pyridyl)cyclobutane. The tetrapyridyl cyclobutane has been synthesized in the organic solid state. The gel forms with a variety of counteranions and gels water. The hydrogel is thixotropic and is composed of nanoscale metal-organic particles (NMOPs), a high surface area of which likely accounts for the gelation of the polar aqueous medium. A shear stress profile of the thixotropic hydrogel gave a yield value of 8.33 Pa. A novel combination of atomic force microscopy (AFM) and scanning transmission X-ray microscopy (STXM) is used to assess the densities of individual NMOPs. A density of 1.37 g/cm3 has been determined. A single-crystal X-ray diffraction study demonstrates the ability of the unsymmetrical cyclobutane 3,4′-tpcb to self-assemble with Cu(II) ions in [Cu2(hfac) 4(3,4′-tpcb)]∞ (where hfac is hexafluoroacetylacetonate) to form a solvated 1D coordination polymer. © 2011 American Chemical Society.