Mechanochemical preparation of copper iodide clusters of interest for luminescent devices

作者:Maini Lucia*; Mazzeo Paolo P; Farinella Francesco; Fattori Valeria; Braga Dario
来源:Faraday Discussions, 2014, 170: 93-107.
DOI:10.1039/c3fd00164d

摘要

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)center dot(CH2Cl2)(0.5)], [CuI(PN)(0.5)](infinity), [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)center dot(CH2Cl2)(0.5)] and [CuI(PN)(3)] while [CuI(PN)(0.5)](infinity) 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.

  • 出版日期2014