Redox-promoted associative assembly of metal–organic materials

Abstract

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.

A chlorine-free protocol for processing germanium

“…Building upon early investigations by El-Hadad et al . ( 25 ) and our recent development of ortho -quinone 1 as a mild and selective metal oxidant ( 9 ) that is readily synthesized from the bulk chemicals phenol and isobutylene ( 26 ), we evaluated the mechanochemical ( 27 ) oxidation of Ge powder (1 equiv) by ball milling with quinone 1 (2 equiv) in the presence of pyridine (Py) (2 equiv) as an auxiliary ligand ( Fig. 2A ).…”

Ball size or ball mass – what matters in organic mechanochemical synthesis?

“…Ball-milling of solid mixtures has proved to be an efficient approach to the synthesis of organic and coordination compounds, ranging from multi-component crystals to polypeptides. [1][2][3][4][5][6][7][8][9][10] In particular, it is becoming increasingly important for obtaining pharmaceutical solids. Mechanochemical methods are attractive as environmentally benign techniques, and often permit rapid and high yield transformations.…”

Chemistry 2.0: Developing a New, Solvent-Free System of Chemical Synthesis Based on Mechanochemistry

“…This was demonstrated by Glavinović and co-workers who utilized ball milling to achieve a redox reaction between zinc, copper or manganese metals and a sterically hindered orthoquinone, leading to rapid and quantitative assembly of metal semiquinonate complexes. 128 In the presence of suitable auxiliary ligands, this leads to multicomponent reactions that yield coordination complexes and polymers through a combination of redox chemistry and coordination-driven self-assembly. The reactivity was subsequently expanded to bulk germanium, 129 leading to facile formation of germanium catecholate complexes, that were used as clean, chlo-…”