Hypersensitive dual-function luminescence switching of a silver-chalcogenolate cluster-based metal–organic framework

Abstract

Silver(i) chalcogenide/chalcogenolate clusters are promising photofunctional materials for sensing, optoelectronics and solar energy harvesting applications. However, their instability and poor room-temperature luminescent quantum yields have hampered more extensive study. Here, we graft such clusters to adaptable bridging ligands, enabling their interconnection and the formation of rigid metal-organic frameworks. By controlling the spatial separation and orientation of the clusters, they then exhibit enhanced stability (over one year) and quantum yield (12.1%). Ultrafast dual-function fluorescence switching (<1 s) is also achieved, with turn-off triggered by O and multicoloured turn-on by volatile organic compounds. Single-crystal X-ray diffraction of the inclusion materials, obtained by single-crystal-to-single-crystal transformation, enables precise determination of the position of the small molecules within the framework, elucidating the switching mechanism. The work enriches the cluster-based metal-organic framework portfolio, bridges the gap between silver chalcogenide/chalcogenolate clusters and metal-organic frameworks, and provides a foundation for further development of functional silver-cluster-based materials.

Strategies for Improving the Performance and Application of MOFs Photocatalysts

“…This kind of materials not only has ultra-high specific surface area, [70][71][72][73] rich topological structure, [74][75][76][77] but high tailorability and designability. They have been extensively studied in the fields of gas adsorption, separation and storage, [78][79][80] fluorescence, [81][82][83] magnetism, [84][85][86][87] and biopharmaceuticals. [88][89][90] Because of their large surface area, it is beneficial to the adsorption of reactants, facilitating catalytic reactions.…”

Magnetic Switching by the In Situ Electrochemical Control of Quasi‐Spin‐Peierls Singlet States in a Three‐Dimensional Spin Lattice Incorporating TTF‐TCNQ Salts

“…[3][4][5] Therea re two methods to use the void spaces (i.e.,p ores)i nM OFs/PCPs:b yp re-organizing functional molecules in the pores during the self-assembly syntheticp rocess (for the design of statically controlled functionality), or by insertingf unctional molecules into the pores after framework formationt oa ttempt the guest-induced dynamic control of the functionality.B ased on the formers trategy,b i -or synergistic functions, such as metallic ferromagnets, [6] chiral magnets, [7,8] and switchable ferroelastic transitions, [9] have been demonstrated, in which functionalities in the framework and the molecules or molecular array in the pores mutuallyi nteract to induce as pecific characteristic. [10] Meanwhile, the latter strategy is acurrent growing interest, in which physical properties of frameworks, such as electronic, [11,12] magnetic, [13][14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30] and spectroscopic properties [31,32] are modulated by guest molecules/ionsi nsertedi nto the nano-sized pores of the frameworks after framework formation.H owever, the development of MOF/PCP materials, where these technical strategies are assembled in as ingle system, is crucial for the creationo fa finely tuned and accessible functional molecular system.F igure 1a shows an example in which at rigger molecule for the activation/inactivationo faframework function is inserted into the pores during the self-assembly process, which inactivates framework function through host-guest interactions (step-A). The trigger molecule is modulated by an externals timulus,o r ac hemical perturbation, to activate the anticipated framework-function (step-B).…”

The Positional Isomeric Effect on the Structural Diversity of Cd(II) Coordination Polymers, Using Flexible Positional Isomeric Ligands Containing Pyridyl, Triazole, and Carboxylate Fragments

“…In this sense, the well-studied luminescent properties [14,15,16,17,18] of d 10 cations, such as Cu(I), Ag(I), and Au(I), as well as their versatility in the construction of complex coordination networks with different types of organic ligands have been the object of interest.…”