Tunable Luminescence in Hybrid Cu(I) and Ag(I) Iodides

Abstract

Hybrid materials are increasingly demonstrating their utility across several optical, electrical, and magnetic applications. Cu(I) halide-based hybrids have attracted attention due to their strong luminescence in the absence of rareearths. Here, we report three Cu(I) and Ag(I) hybrid iodides with 1,5-naphthyridine, and additional triphenylphosphine (Ph3P) ligands. The compounds are built on (Cu/Ag)-I staircase chains or on a rhomboid Cu2I2 dimer and display intense and tunable luminescence. Replacing Cu with Ag, and adding the second kind of organic ligand (Ph3P) tunes the emission color from red to yellow and results in significantly enhanced quantum yield. Density functional theory-based electronic structure calculations reveal the separate effects of the inorganic module and organic ligand on the electronic structure, confirming that bandgap, optical absorption and emission properties of these phosphors can be systemically and deliberately tuned by metal substitution and organic ligands cooperation. The emerging understanding of composition-structureproperty relations in this family provides powerful design tools towards new compounds for general lighting applications.Crystallographic details for Compound 1-3. The Supporting Information is available free of charge via the Internet at http://pubs.acs.org.

Ligand Control of Structural Diversity in Luminescent Hybrid Copper(I) Iodides

“…[19][20][21][22][23] Copper(I) iodide hybrids are of particular interest, and regarded as promising for next generation lighting technologies because of their unique properties including structural diversity, optical tunability, and superior luminescence performance. [24][25][26][27][28] Aside from the diversity of the organic components, the charge-neutral inorganic motif CumIm takes various forms ranging from zero-dimensional (0D) discrete clusters 29 to one-dimensional (1D) extended chains, 30 two-dimensional (2D) layers, 31 and three-dimensional (3D) networks 32 with the most common inorganic modules being CuI monomer, [33][34][35] CuI 1D chains, [36][37][38] Cu2I2 rhomboid dimer, [39][40][41] and Cu4I4 cubane tetramers. [42][43][44] The CuxIxLy complexes (L = N-, P-, S-, Sb-or Se-doner ligands) with Cu3I3 trimer, 45,46 octahedral Cu4I4 tetramer, [47][48][49] Cu4I4 staircase tetramer, 50 and Cu6I6 cubane hexamer 51,52 as inorganic modules are also reported.…”

“…45,48,49,[53][54][55][56][57][58][59][60][61][62] The various inorganic modules in conjunction with the diverse organic ligands via coordinate bonds give rise to rich hybrid copper (I) iodide structures of various dimensionalities (0D-3D), which provide a solid foundation for their tunable luminescence with emission covering the entire visible range and NIR edge. 24,38,40 With the aim of further exploring the structural diversity and luminescence properties of copper (I) iodide hybrids, we report here ten new compounds, focusing on their composition-structure-property correlations. These new structures present a library that includes CuI 1D chain structures, Cu2I2 rhomboid dimer structures, Cu4I4 cubane tetramer structures, and octahedral Cu4I4 tetramer structures.…”

A cluster-based phosphor against thermal quenching via dynamic metallic bonding

“…These intermolecular interactions synergistically rigidify the metal-organic framework, which favors the additional structural stability at high temperatures. [45][46][47][48][49][50][51] Both single-crystal and powder XRD patterns of bppCu 4 I 4 P 4 revealed a reversible structural transformation with changing temperature (Fig. 2a and Supplementary Fig.…”

Zero-dimensional plate-shaped copper halide crystals with green-yellow emissions

“…[22][23][24] By contrast, recently, Cu-based 0D OIMHs compounds have been reported by the formation of the ionic complex in copper hybrid materials, instead of a coordination complex, 25 which exhibit high PL quantum yields (PLQYs) and excellent stability. 26,27 Unfortunately, much effort was mainly devoted to the fabrication of bulk OIMHs compounds, no study is carried out on the control of their external morphologies.…”