Metal-organic complexes assembled from coordinative interactions are known to be able to display a wide range of photoluminescent behaviors benefiting from an extensive number of metal ions, organic linkers, and inclusion guests, depending on the multifaceted nature of their chemical structures and photophysical properties. In the past two decades, the white-light-emitting (WLE) and photoluminescent color-tuning (PLCT) materials based on the single-phase metal-organic coordination assemblies have merited particular attention and gained substantial advances. In this review, we give an overview of recent progress in this field, placing emphasis on the WLE and PLCT properties realized in the single-phase materials, which covers the origin, generation, and manipulation of different types of photoluminescence (PL) derived from ligand-centered (LC), metal/cluster-centered (MC or CC), excimer/exciplex-based (EX), metal-to-ligand or ligand-to-metal charge-transfer-based (MLCT or LMCT), or guest-included emissions. The coordination assemblies in this topic can be generally classified into three categories [(1) mono/homometallic coordination assemblies based on main group (s,p-block), transition (d-block), or lanthanide (f-block) metal centers, (2) s/p-f-, d-f-, or f-f-type heterometallic coordination assemblies, and (3) guest-included coordination assemblies] for which WLE and PLCT properties can be achieved by virtue of either a wide-band/overlapped emission covering the whole visible spectrum from a single emitting center or a combination of complementary color emissions from multiple emitting centers/origins. Some state-of-the-art assembly methods and successful design models relevant to the above three categories are elaborated to demonstrate how to achieve efficient and controllable white-light emission in a single-phase material through a tunable PL approach. Potential applications in the fields of lighting and displaying, sensing and detecting, and barcoding and patterning are surveyed, and at the end, possible prospects and challenges for future development along this line are proposed.
Two-dimensional (2D) metal–organic frameworks have exhibited a range of fascinating attributes, of interest to numerous fields. Here, a calcium-based metal-organic framework with a 2D layered structure has been designed. Dual emissions relating to intralayer excimers and interlayer trapped excitons are produced, showing excitation-dependent shifting tendency, characteristic of a low dimensional semiconductor nature. Furthermore, the layer stacking by weak van der Waals forces among dynamically coordinated DMF molecules enables exfoliation and morphology transformation, which can be achieved by ultrasound in different ratios of DMF/H2O solvents, or grinding under appropriate humidity conditions, leading to nano samples including ultrathin nanosheets with single or few coordination layers. The cutting down of layer numbers engenders suppression of interlayer exciton-related emission, resulting in modulation of the overall emitting color and optical memory states. This provides a rare prototypical model with switchable dual-channel emissions based on 2D-MOFs, in which the interlayer excitation channel can be reversibly tuned on/off by top-down exfoliation and morphology transformation.
Four Ru/Rh half-sandwich units are incorporated into UiO-67 frameworks by post-synthetic exchange (PSE) method, and employed for photocatalytic H2 evolution and CO2 reduction.
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