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A series of all-in-one (AIO) type copper halide based luminescent inorganic-organic hybrid semiconductors have been synthesized and characterized. The study offers insights into the structure-property relationships in this material family.

We present 1D CuI-based polymers exhibiting remarkable short-lived TADF and phosphorescence induced by photo- or X-ray irradiation.

We present a unique new subclass of Cu(i) hybrid complexes, showing TADF with near-unity quantum yields as well as unprecedented solvatochromic emission and strong X-ray radioluminescence.

Inorganic-organic hybrid luminescent materials have received great attention for their potential applications in a wide range of clean/renewable energy-related areas, including photovoltaics and solid-state lighting. Herein, we present a unique and general "Mn + Cu" approach by blending two earth-abundant luminogenic metals, manganese and copper, within a single ionic structure to construct a remarkable family of low-cost and multifunctional hybrid materials featuring dual emission, as well as triboluminescence and second-harmonic generation response. The novel hybrid materials are made of diphosphine dioxide-chelated [Mn(O∧O)

Two photoluminescent copper(I) iodide inorganic-organic hybrid materials have been synthesized and structurally characterized as 1D-Cu2I2(bpoe)2 (1) and 1D-Cu2I2(bbtpe-m)2 (2) (bpoe = 1,2-bis(pyridin-3-yloxy)ethane, bbtpe-m = 1,1′-(3-methylpentane-1,5-diyl)bis(1H-benzo[1,2,3]triazole). Both are chain-like structures composed of Cu2I2 rhomboid dimers connected by bidentate ligands. Their emission colors range from cyan to yellow with relatively high internal quantum yields in the solid state. The tunable band gap and emission color is achieved by varying the LUMO energies of the ligands. The structures are robust and remain stable up to T = 260 °C, and coupled with their efficient and adjustable luminescence, facile synthesis, and non-toxic nature, these compounds demonstrate potential as rare earth element (REE)-free phosphors.

The CuI-derived inorganic–organic hybrid compounds are considered as promising phosphors for the lighting industry. Herein, exploiting N-monoalkylated hexaminium salts, [R-HMTA]X (R = Me, Et, Pr, a...

A series of copper halide based inorganic–organic hybrid semiconductors have been synthesized. Structural analysis confirms that all compounds are composed of one-dimensional Cu4X62− anionic chains that coordinate to cationic ligands via Cu–N dative bonds. Different coordination affinities of the ligands lead to two types of ligand arrangements with various structural distortions. All compounds are highly resistant to heat and moisture as a result of the combination of coordinate and ionic bonds. Low energy emission with high efficiency is achieved for these compounds and the emission energy (∼552–615 nm) and color (yellow-orange) can be tuned by varying the ligand and halogen element. The electronic structure and luminescence mechanism are examined by both experimental and theoretical methods. More importantly, all compounds demonstrate good solubility in polar aprotic solvents, a desired property that is absent in all other CuX hybrid families of extended structures, which is attributed primarily to the ionic nature of this material class. The good solution-processability, and cost effective and easily scalable synthesis coupled with high quantum efficiencies and framework stability make these hybrid materials promising phosphors for general lighting applications.

Fluorosis has been regarded as a worldwide disease that seriously diminishes the quality of life through skeletal embrittlement and hepatic damage. Effective detection and removal of fluorinated chemical species such as fluoride ions (F−) and perfluorooctanoic acid (PFOA) from drinking water are of great importance for the sake of human health. Aiming to develop water-stable, highly selective and sensitive fluorine sensors, we have designed a new luminescent MOF In(tcpp) using a chromophore ligand 2,3,5,6-tetrakis(4-carboxyphenyl)pyrazine (H4tcpp). In(tcpp) exhibits high sensitivity and selectivity for turn-on detection of F− and turn-off detection of PFOA with a detection limit of 1.3 μg L−1 and 19 μg L−1, respectively. In(tcpp) also shows high recyclability and can be reused multiple times for F− detection. The mechanisms of interaction between In(tcpp) and the analytes are investigated by several experiments and DFT calculations. These studies reveal insightful information concerning the nature of F− and PFOA binding within the MOF structure. In addition, In(tcpp) also acts as an efficient adsorbent for the removal of F− (36.7 mg g−1) and PFOA (980.0 mg g−1). It is the first material that is not only capable of switchable sensing of F− and PFOA but also competent for removing the pollutants via different functional groups., A robust In-MOF, In(tcpp), demonstrates sensitive detection of the fluorinated chemical species F− and PFOA via distinctly different luminescence signal change, and effective adsorption and removal of both species from aqueous solution.

Conventional inorganic semiconductors are best known for their superior physical properties and chemical robustness, and their widespread use in optoelectronic devices. However, implementation of these materials in many other applications has been hindered by their poor solubility and/or solution-processability, a longstanding drawback that is largely responsible for issues such as high cost. While recent progress on hybrid perovskites, an important class of inorganic–organic hybrid materials, has shed light on the development of high-performance solution processable semiconductors, they rely heavily on toxic metals and generally suffer from framework instability. To address these issues, a new group of hybrid semiconductors based on anionic copper(i) halide and cationic organic ligands has been developed. These compounds are noted as All-In-One (AIO) structures as they consist of covalently bonded anionic CuX inorganic modules that form both coordinate and ionic bonds with cationic organic ligands. Studies demonstrate that framework stability and solution processibility of these materials are greatly enhanced as a result of such bonds. In the perspective, we highlight the development of this newly emerged type of materials including their crystal structures, chemical and physical properties and possible applications. The untapped potential that the AIO approach can offer for other hybrid families is also discussed., This Perspective features the newly emerged AIO-type Cu(i)X-based hybrid semiconductors and showcases their structural diversity, solution-processability, framework stability, important photophysical properties and related potential applications.

Inorganic semiconductor materials are best known for their superior physical properties, as well as their structural rigidity and stability. However, the poor solubility and solution-processability of these covalently bonded network structures has long been a serious drawback that limits their use in many important applications. Here, we present a unique and general approach to synthesize robust, solution-processable, and highly luminescent hybrid materials built on periodic and infinite inorganic modules. Structure analysis confirms that all compounds are composed of one-dimensional anionic chains of copper iodide (CumIm+22-) coordinated to cationic organic ligands via Cu-N bonds. The choice of ligands plays an important role in the coordination mode (μ1-MC or μ2-DC) and Cu-N bond strength. Greatly suppressed nonradiative decay is achieved for the μ2-DC structures. Record high quantum yields of 85% (λex = 360 nm) and 76% (λex = 450 nm) are obtained for an orange-emitting 1D-Cu4I6(L6). Temperature dependent PL measurements suggest that both phosphorescence and thermally activated delayed fluorescence contribute to the emission of these 1D-AIO compounds, and that the extent of nonradiative decay of the μ2-DC structures is much less than that of the μ1-DC structures. More significantly, all compounds are remarkably soluble in polar aprotic solvents, distinctly different from previously reported CuI based hybrid materials made of charge-neutral CumXm (X = Cl, Br, I), which are totally insoluble in all common solvents. The greatly enhanced solubility is a result of incorporation of ionic bonds into extended covalent/coordinate network structures, making it possible to fabricate large scale thin films by solution processes.