Interpenetration (catenation) has long been considered a major impediment in the achievement of stable and porous crystalline structures. A strategy for the design of highly porous and structurally stable networks makes use of metal-organic building blocks that can be assembled on a triply periodic P-minimal geometric surface to produce structures that are interpenetrating-more accurately considered as interwoven. We used 4,4',4"-benzene-1,3,5-triyl-tribenzoic acid (H(3)BTB), copper(II) nitrate, and N,N'-dimethylformamide (DMF) to prepare Cu(3)(BTB)(2)(H(2)O)(3).(DMF)(9)(H(2)O)(2) (MOF-14), whose structure reveals a pair of interwoven metal-organic frameworks that are mutually reinforced. The structure contains remarkably large pores, 16.4 angstroms in diameter, in which voluminous amounts of gases and organic solvents can be reversibly sorbed.
The precipitation of barium or strontium carbonates in alkaline silica-rich environments leads to crystalline aggregates that have been named silica/carbonate biomorphs because their morphology resembles that of primitive organisms. These aggregates are self-assembled materials of purely inorganic origin, with an amorphous phase of silica intimately intertwined with a carbonate nanocrystalline phase. We propose a mechanism that explains all the morphologies described for biomorphs. Chemically coupled coprecipitation of carbonate and silica leads to fibrillation of the growing front and to laminar structures that experience curling at their growing rim. These curls propagate in a surflike way along the rim of the laminae. We show that all observed morphologies with smoothly varying positive or negative Gaussian curvatures can be explained by the combined growth of counterpropagating curls and growing laminae.
We have synthesized inorganic micron-sized filaments, whose microstucture consists of silica-coated nanometer-sized carbonate crystals, arranged with strong orientational order. They exhibit noncrystallographic, curved, helical morphologies, reminiscent of biological forms. The filaments are similar to supposed cyanobacterial microfossils from the Precambrian Warrawoona chert formation in Western Australia, reputed to be the oldest terrestrial microfossils. Simple organic hydrocarbons, whose sources may also be abiotic and indeed inorganic, readily condense onto these filaments and subsequently polymerize under gentle heating to yield kerogenous products. Our results demonstrate that abiotic and morphologically complex microstructures that are identical to currently accepted biogenic materials can be synthesized inorganically.
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