New Approach toward Dual-Emissive Organic–Inorganic Hybrids by Integrating Mn(II) and Cu(I) Emission Centers in Ionic Crystals

Abstract

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)3]2+ cations and various anionic [Cu x I y ](y−x)– clusters, ensuring manifestation of dual phosphorescence streamed from octahedral Mn2+ ions (605–648 nm) and iodocuprate anions (480–728 nm). Noteworthily, the relative ratio of the emission bands, and hence a resulting emission chromaticity, can be tuned in a wide range through modification of cluster [Cu x I y ](y−x)– modules. The structural diversity, enhanced robustness, and up to 100% luminescence quantum yield make the designed materials promising phosphors for lighting and sensing applications.

Dual-ligand-functionalized dodeca-nuclear lanthanide–tungsten-cluster incorporated selenotungstates and fluorescence detection of dipicolinic acid (an anthrax biomarker)

“…For example, the sensitization of lanthanide emissions by organic chromophores can play an important role in developing function-oriented structural assembly, functional complementation and performance optimization. [3][4][5] Polyoxometalates (POMs) are a class of inorganic metal-oxo clusters and have exhibited their rich architectural diversity and fascinating properties in optics, catalysis, magnetism, biomedicine, nanotechnology, etc. [6][7][8][9][10][11] As the most widely researched branch of POMs, polyoxotungstates (POTs), particularly inorganic-organic hybrid POT materials (IOHPMs), have attracted ongoing research interest.…”

“…For example, the sensitization of lanthanide emissions by organic chromophores can play an important role in developing function-oriented structural assembly, functional complementation and performance optimization. 3–5…”

Engineering of metal–organic frameworks (MOFs) for thermometry

“…[9][10][11][12][13][14][15] MOFs are porous materials that are assembled from the connection between a metal ion (metal node or SBU) and an organic ligand. MOFs possess several crucial structural features, such as a regular organic-inorganic network, 16,17 high crystallinity, 18 porosity, 19,20 flexibility, 21,22 stability, 23 hostguest interaction capability 24 and easy functionalization 25 with tuneable pore size. 26 These features make them amenable to numerous potential applications, including sensing, [27][28][29][30] catalysis, 31,32 gas adsorption and sequestration, [33][34][35] separation, 36 and bio-application.…”

Assembly of One-, Two-, and Three-Dimensional Cu(I)-Based Coordination Frameworks for Tunable White Light Emission and Effective Fluorescence Sensing

“…Luminescent coordination polymers (CPs) have received huge attention by virtue of their diverse topologies and broad applications in optics, display, bioimaging, sensing, and detection. − Of particular interest is the family of d 8 /d 10 transition-metal compounds, which is regarded as an emerging class of excellent luminescent solids benefiting from the presence of noncovalent metal···metal interactions in such complexes. − In particular, the copper­(I) halide-based coordination compounds, owing to not only the diverse coordination styles of Cu + (linear, trigonal, and tetrahedral geometry) and halide anions (from μ 2 - to μ 8 -linking) but also their unique photophysical or photochemical properties, have attracted huge interest. − Consequently, great efforts are being made in the pursuit of Cu-X-based (X = I, Br, Cl) networks with diverse structural motifs varying from discrete CuX or CuX 2 , Cu 2 X 2 dimers, Cu 3 X 3 , Cu 4 X 4 , or Cu 6 X 6 clusters, to zigzag [CuX] n or double-stranded [Cu 2 X 2 ] n chains and even to 2D Cu-X-based layers or 3D intricate frameworks. − Thanks to these various building blocks in the self-assembly process, numerous copper­(I) halide-based coordination frameworks have been fabricated in recent years with the assistance of diverse bridging ligands, which have a large possibility to exhibit vivid luminescence rooted in cluster-centered interactions or intracluster metal-halide charge transfer. , For example, Zang and co-workers reported a copper iodide cluster-based metal–organic framework (MOF) scintillator, which presents a high X-ray excited luminescence efficiency and can be used for X-ray flexible imaging …”