Microporous Metal-Phosphonates with a Novel Orthogonalized Linker and Complementary Guests: Insights for Trivalent Metal Complexes from Divalent Metal Complexes.

The reliable self-assembly of microporous metal-phosphonate materials remains a longstanding challenge. This stems from, generally, more coordination modes for the functional group allowing more dense structures, and stronger bonding driving less crystalline products. Here, a novel orthogonalized aryl-phosphonate linker, 1,3,5-tris(4'-phosphono-2',6'-dimethylphenyl) benzene (H L3) has been used to direct formation of open frameworks.

Orthogonalization of Polyaryl Linkers as a Route to More Porous Phosphonate Metal-Organic Frameworks.

The coordinative pliancy of the phosphonate functional group means that metal-phosphonate materials often self-assemble as well-packed structures with minimal porosity, as efficient inter-ligand packing is enabled. Here, we report a multistep synthesis of a novel aryl-phosphonate linker with an orthogonalized ligand core, 1,3,5-tris(4'-phosphonophenyl)-2,4,6-trimethylbenzene (H L2) designed to form more open structures. A series of crystalline metal-phosphonate frameworks (CALF-35 to -39) have been assembled by coordinating to divalent metals (Ba, Sr, Ca, Mg, Zn).

A chlorine-free protocol for processing germanium.

Replacing molecular chlorine and hydrochloric acid with less energy- and risk-intensive reagents would markedly improve the environmental impact of metal manufacturing at a time when demand for metals is rapidly increasing. We describe a recyclable quinone/catechol redox platform that provides an innovative replacement for elemental chlorine and hydrochloric acid in the conversion of either germanium metal or germanium dioxide to a germanium tetrachloride substitute. Germanium is classified as a "critical" element based on its high dispersion in the environment, growing demand, and lack of suitable substitutes.

Redox-promoted associative assembly of metal-organic materials.

We develop an associative synthesis of metal-organic materials that combines solid-state metal oxidation and coordination-driven self-assembly into a one-step, waste-free transformation. The methodology hinges on the unique reactivity of -quinones, which we introduce as versatile oxidants for mechanochemical synthesis. Our strategy opens a previously unexplored route to paramagnetic metal-organic materials from elementary metals.