Copper Iodide Clusters Research Articles

Hard/Soft Heterometallic Network Complex of a Macrocycle with Endo/Exocyclic Coordination

One-pot assembly reactions of an S(2)O(4) macrocycle with CuI in the absence and presence of KI afforded an emissive one-dimensional looped coordination polymer linked with a cubane-type copper iodide cluster and an endocoordinated potassium(I) coordination polymer linked with a ribbon-type copper iodide cluster, respectively.

Mechanochromic and Thermochromic Luminescence of a Copper Iodide Cluster

The mechanochromic and thermochromic luminescence properties of a molecular copper(I) iodide cluster formulated [Cu(4)I(4)(PPh(2)(CH(2)CH=CH(2)))(4)] are reported. Upon mechanical grinding in a mortar, its solid-state emission properties are drastically modified as well as its thermochromic behavior. This reversible phenomenon has been attributed to distortions in the crystal packing leading to modifications of the intermolecular interactions and thus of the [Cu(4)I(4)] cluster core geometry. Notably, modification of the Cu-Cu interactions seems to be involved in this phenomenon directly affecting the emissive properties of the cluster.

Unsymmetrical Calixcrowns Incorporating Hard and Soft Loops as a New Scaffold for Multinuclear Endo/Exocyclic Complexation and Networking

Unsymmerical calix[4]crowns containing [(O(4)S)(O(5))] (L(1)) and [(O(4)S(2))(O(5))] (L(2)) as crown loops were employed as new scaffolds both for complexation studies and for network formation. Reactions of L(1) and L(2) with KI in the presence of CuI afforded a copper(I) iodide cluster linked 1D-type endocyclic dipotassium(I) complex [K(2)(L(1))(Cu(7)I(9))](n) (1) and a copper(I) iodide cluster linked 1D-type endocyclic monopotassium(I) complex [KL(2)(mu(2)-Cu(3)I(4))](n) (2), respectively. By comparison, the reaction of L(2) with KPF(6) in the presence of CuI and HgI(2) afforded the 1-D endocyclic potassium(I) complex [K(L(2))(CuHgI(4))](n) (3), linked with a CuHgI(4) cluster unit. The formation of homo- and heterodinuclear complexes in solution was also confirmed by comparative NMR studies.

Synthesis and sol–gel assembly of nanophosphors

Some recent works made in our group on inorganic nanophosphors are briefly reviewed in this paper. We first present the synthesis of highly concentrated semiconductor quantum dot colloids allowing the extension of the well-known oxide sol–gel process to chalcogenide compounds. Secondly, we show the synthesis and the chemical functionalization of lanthanide-doped insulator nanoparticles. In particular, the annealing process of these particles at high temperature leads to highly bright nanocrystals, which can be used as biological luminescent labels or for integration in transparent luminescent coatings. Finally, we consider luminescent transition metal clusters, which combine the inorganic structure of nanoparticles with the monodispersity and the easy functionalization of the organic molecules. Emphasis is put on the original thermochromic luminescence properties of copper iodide clusters trapped in siloxane-based films. Nous présentons une brève revue du travail de notre groupe concernant les nanoémetteurs de lumière. Dans une première partie, nous présentons la synthèse de colloïdes concentrés de particules de semi-conducteurs, permettant d’étendre les principes du procédé sol–gel d’oxydes aux matériaux de type chalcogénures. Nous montrons ensuite la synthèse et la fonctionnalisation de nanoparticules d’oxydes dopées lanthanides. Un traitement à haute température de ces particules permet d’obtenir des nanocristaux à haut rendement de luminescence utilisables comme marqueurs biologiques ou dans des revêtements transparents luminescents. Finalement, nous considérons les clusters de métaux de transition qui combinent la structure minérale des nanoparticules avec la monodispersité et la facilité de fonctionnalisation des molécules organiques. On s’intéresse en particulier au thermochromisme des clusters d’iodure de cuivre piégés dans des films sol–gel à base de silice.

Thermochromic Luminescence of Sol−Gel Films Based on Copper Iodide Clusters

The incorporation of copper iodide clusters in sol−gel silica has been investigated to prepare materials with original luminescent properties. The synthesis, structural characterizations, and optical properties of sol−gel films containing [Cu4I4L4] clusters, L = phosphine-based ligands, are reported. Clusters studied are [Cu4I4(PPh2(CH2)2Si(OCH2CH3)3)4] (C1), able to copolymerize with the silica matrix, and [Cu4I4(PPh2(CH2)2CH3)4] (C2) used as a reference for the characterizations. The luminescent films exhibit the optical properties of these clusters in accordance with XPS and NMR studies demonstrating their integrity in the gel matrix. The temperature dependence of light emission properties of clusters and films shows, for the first time for phosphine-based [Cu4X4L4] clusters, thermochromic luminescence with bright yellow luminescence at room temperature and purple emission at 77 K. As a result of weak Cu−Cu interactions, the two emissive states appear as highly coupled with a low energy barrier (2 kJ·m...

Synthesis and Crystal Structures of Novel Copper(I) Complexes of a Phosphanylborane

AbstractThe novel copper iodide clusters [Cu3(μ‐I)(μ3‐I)2(PH2BH2·NMe3)3] (2) and [Cu4(μ‐I)2(μ3‐I)2(PH2BH2·NMe3)3] (3) were synthesized by treating CuI with the primary phosphine (H2PBH2·NMe3). The novel features of both compounds, which have been characterized by X‐ray crystallography, are the unsymmetrical constitution of the copper iodide core due to the influence of the monodentate phosphorus ligand. This results in copper atoms with different coordination numbers within the compound. Complex 2, the major product of the reaction, contains a distorted octahedral Cu3I3‐core, in which one vertex is missing. Complex 3 was isolated as a by‐product and is composed of a Cu4I4‐core in a distorted octahedral coordination.

Syntheses, Crystal Structure and Luminescent Properties of Co-ordination Networks Based on Copper(I) Iodide Clusters from 1, 4-Bis(imidazole-1-ylmethyl)benzene

This paper presents novel and distinctive Copper(I) iodide polymers with intriguing structure motifs, constructed from 1, 4-bis(imidazole-1-ylmethyl)benzene (bix). Treatment of bix with CuI generated [(Cu4I4)(bix)2]n1, whose X-ray single crystal structural determination revealed a novel 2-D battlement-like sheet structure with square grids based on distorted cubane-like Cu4I4 clusters. The structural features and photoluminescence of the complexes are discussed. The present finding may provide insight into the coordination versatility of copper(I) halide clusters with N-donor ligands and an inspiration for the self-assembly of novel supramolecular networks based on copper(I) halide clusters.