Synthesis of Oligodiacetylene Derivatives from Flexible Porous Coordination Frameworks.

Oligodiacetylenes (ODAs) with alternating ene-yne conjugated structure are significant materials for optical and electronic properties. Due to the low solubility of ODAs in common solvents, the synthetic approaches are limited. Here we disclose a new synthetic approach of ODAs without a side alkyl chain using a porous coordination polymer (PCP) as a sacrificial template. 1,2-Bis(4-pyridyl)butadiyne, which works as a monomer, was embedded in the flexible framework of the PCP, and ODAs were synthesized via utilization of the anisotropic thermal expansion of the PCP crystal. The oligomeric state of ODAs depends on the metal ion and coligand of the precursor.

Formation of Foam-like Microstructural Carbon Material by Carbonization of Porous Coordination Polymers through a Ligand-Assisted Foaming Process.

Porous carbon material with a foam-like microstructure has been synthesized by direct carbonization of porous coordination polymer (PCP). In situ generation of foaming agents by chemical reactions of ligands in PCP during carbonization provides a simple way to create lightweight carbon material with a foam-like microstructure. Among several substituents investigated, the nitro group has been shown to be the key to obtain the unique foam-like microstructure, which is due to the fast kinetics of gas evolution during carbonization. Foam-like microstructural carbon materials showed higher pore volume and specific capacitance compared to a microporous carbon.

Iron-catalyzed cross-coupling of alkyl sulfonates with arylzinc reagents.

Iron-catalyzed cross-coupling reactions of primary and secondary alkyl sulfonates with arylzinc reagents proceed smoothly in the presence of excess TMEDA and a concomitant magnesium salt. The arylzinc reagents are prepared from the corresponding aryllithium or magnesium reagents with ZnI(2). The in situ formation of alkyl iodides and consecutive rapid cross-coupling avoids discrete preparation of the unstable secondary alkyl halides and also achieves high product selectivity.

Iron-catalysed fluoroaromatic coupling reactions under catalytic modulation with 1,2-bis(diphenylphosphino)benzene.

A catalytic amount of 1,2-bis(diphenylphosphino)benzene (DPPBz) achieves selective cleavage of sp(3)-carbon-halogen bond in the iron-catalysed cross-coupling between polyfluorinated arylzinc reagents and alkyl halides, which was unachievable with a stoichiometric modifier such as TMEDA; the selective iron-catalysed fluoroaromatic coupling provides easy and practical access to polyfluorinated aromatic compounds.