Several important solvothermal (including hydrothermal) in situ metal/ligand reactions and their mechanisms, including dehydrogenative carbon−carbon coupling, hydroxylation of aromatic rings, cycloaddition of organic nitriles with azide and ammonia, transformation of inorganic and organic sulfur, as well as the CuII to CuI reduction, are outlined in this Account. The current progress clearly demonstrates the important potential of such reactions in the crystal engineering of functional coordination compounds and one-pot synthesis of some unusual organic ligands that are inaccessible or not easily obtainable via conventional methods, thereby substantiating our expectation that a new bridge has been created between coordination chemistry and synthetic organic chemistry.

Solvothermal in situ metal/ligand reactions: a new bridge between coordination chemistry and organic synthetic chemistry.

Hydro(solvo)thermal in situ ligand syntheses

Copper(I) halides: A versatile family in coordination chemistry and crystal engineering

Crystal engineering is the rational design and assembly of solid-state structures with desired properties via the manipulation of intermolecular interactions, hydrogen bonding and metal–ligand complexation in particular. The heart of crystal engineering is to control the ordering of the building blocks, be they molecular or ionic, toward a specific disposition in the solid state. The relatively weak strength of intermolecular forces with respect to chemical bonding renders the assembly of supramolecular constructs sensitive to external physical and chemical stimuli, with pH condition of the reaction mixture being arguably the most prominent and extensively observed. Using selected examples of constructing metal–organic architectures from recent literature, the influences of pH on the specific ligand forms, the generation and metal coordination of hydroxo ligands, ligand transformation promoted by pH condition changes, pH-dependent kinetics of crystallization of a number of metal–organic architectures are discussed. Current status of this particular areas of research in supramolecular chemistry and materials are assessed and personal perspectives as to toward what directions should this chemistry head are elaborated.

pH effect on the assembly of metal-organic architectures

Solvothermal synthesis of Group 13–15 chalcogenidometalates with chelating organic amines

A simultaneous redox, alkylation, self-assembly reaction under solvothermal conditions afforded a novel copper(I) chain polymer constructed of luminescent Cu3I4- and unprecedented EtS-4-C5H4N+Et components (Et = CH3CH2).

A simultaneous redox, alkylation, self-assembly reaction under solvothermal conditions afforded a luminescent copper(I) chain polymer constructed of Cu3I4- and EtS-4-C5H4N+Et components (Et = CH3CH2).

Ye Yan Qin

Papers

A simultaneous redox, alkylation, self-assembly reaction under solvothermal conditions afforded a luminescent copper(I) chain polymer constructed of Cu3I4- and EtS-4-C5H4N+Et components (Et = CH3CH2).