Mechanochemical preparation of copper iodide clusters of interest for luminescent devices

Abstract

The copper iodide complexes are known for their large variety of coordination geometries. Such diversity, while making it difficult to predict the final structure, permits the preparation of a great number of copper iodide complexes based on the same ligand. The target of the research was that of thoroughly exploring the chemistry of CuI and the ligand diphenyl-2-pyridyl phosphine (PN) by varying the stoichiometric ratio and/or the aggregation state. Six different compounds have been identified: [Cu4I4(PN)2], [Cu4I4(PN)2·(CH2Cl2)0.5], [CuI(PN)0.5]∞, [CuI(PN)3] whose structures have been determined during this study, CuI(PN)2 which was characterized by powder diffraction and [Cu2I2(PN)3] which has been already reported. The preparation routes are also different: synthesis in solution yielded [Cu4I4(PN)2·(CH2Cl2)0.5] and [CuI(PN)3] while [CuI(PN)0.5]∞ and CuI(PN)2 were obtained only via solid state reactions. These two latter examples confirmed that mechanochemistry is a valid route to explore the landscape of the possible structures of CuI derivatives. Crystallization by traditional solution procedures failed to give the desired crystal, so structure determination of the new compounds was tackled in two ways: by attempting crystal growth via solvothermal synthesis and by resolving the structure from X-ray powder diffraction data with "direct space" methods. What is more the photophysical properties of the complexes that could be obtained as sufficiently pure powders have also been investigated and are reported herein.

Systematic studies on mechanochemical synthesis: Schiff bases from solid aromatic primary amines and aldehydes

“…In a recent Faraday discussion‐themed issue on “ Mechanochemistry: From Functional Solids to Single Molecules, ” the mechanochemistry of organic molecules, soft materials and pharmaceuticals, the mechanochemistry of inorganic compounds and coordination‐based materials, sonication and macromolecular mechanochemistry, current theoretical models for mechanochemical reactions, the mechanistic and kinetic understanding, catalysis, and scaling up of mechanochemistry were broadly discussed …”

Dual luminescence in solid CuI(piperazine): hypothesis of an emissive 1-D delocalized excited state

“…[1][2][3][4][5] They are easily synthesized 6,7 and tunable in emission color, [8][9][10] with high emission quantum yields in the solid state. 7,10,11 Copper(I) halide compounds can be considered as a valid alternative to luminescent metal complexes of precious (i.e.…”

Chapter 7. Ball-milling Mechanochemical Synthesis of Coordination Bonds: Discrete Units, Polymers and Porous Materials

“…The luminescent properties of the prepared materials polymers arise from the presence of Cu 2 I 2 dimeric units that are separated by organic ligands so as to form 2D frameworks. 94 The mechanochemical syntheses provided a clear benefit over conventional solution syntheses by allowing the direct use of copper(I) iodide precursor whose application in conventional solution-based synthesis is often complicated due to poor solubility. This work was subsequently extended towards the synthesis of discrete luminescent complexes by grinding of copper(I) iodide with the bidentate ligand diphenyl(2-pyridyl)phosphine (dpn) by LAG.…”