The exploration of solvent-driven reversible structural transformation in clusters is crucial for advanced stimulus-responsive optical applications and understanding of structure-property relationships.Herein,we repor...The exploration of solvent-driven reversible structural transformation in clusters is crucial for advanced stimulus-responsive optical applications and understanding of structure-property relationships.Herein,we report a solvent-driven reversible trans-formation between two copper(I)clusters:[Cu(totp)(CH_(3)CN)_(3)][Cu_(2)I_(3)(totp)(DPPPy)]·CH_(3)CN 1 and Cu_(4)I_(4)(DPPPy)_(2)·0.5CH_(2)Cl_(2)2(totp=tri-o-tolylphosphine,DPPPy=2-[diphenylphosphino]pyridine).X-ray radioluminescence and encryption applications were studied based on structure-dependent photophysical properties difference.The noncovalent interaction-mediated space charge transition between isolated ion units of 1 enables more efficient thermally activated delayed fluorescence by reverse intersystem crossing,accounting for structure-dependent luminescence.Notably,compared to 2,1 exhibits a higher scintillation light yield of 14832 photons MeV^(-1),exceeding that of the commercial scintillator Bi_(4)Ge_(3)O_(12)(8000 photons MeV^(-1)),and a low X-ray detection limit of 22.49 nGy s^(-1),far below the typical diagnostic dose(5.5μGy s^(-1)).Furthermore,scintillating film fabricated by 1 achieves X-ray imaging with a high spatial resolution of 16 lp/mm.The reversible structural interconversion enables solvent-responsive luminescent switches,and thus,the dynamic encryption system capable of multistage decryption was developed.This work not only offers new insight into solvent-regulated clusters transformations but also provides a promising strategy for developing high-performance copper(I)clusters-based scintillators and stimulus-responsive optical devices.展开更多
基金supported by the National Natural Science Foundation of China(21971240 and 22271283)the Natural Science Foundation of Shandong Province(ZR2025QC1361)。
文摘The exploration of solvent-driven reversible structural transformation in clusters is crucial for advanced stimulus-responsive optical applications and understanding of structure-property relationships.Herein,we report a solvent-driven reversible trans-formation between two copper(I)clusters:[Cu(totp)(CH_(3)CN)_(3)][Cu_(2)I_(3)(totp)(DPPPy)]·CH_(3)CN 1 and Cu_(4)I_(4)(DPPPy)_(2)·0.5CH_(2)Cl_(2)2(totp=tri-o-tolylphosphine,DPPPy=2-[diphenylphosphino]pyridine).X-ray radioluminescence and encryption applications were studied based on structure-dependent photophysical properties difference.The noncovalent interaction-mediated space charge transition between isolated ion units of 1 enables more efficient thermally activated delayed fluorescence by reverse intersystem crossing,accounting for structure-dependent luminescence.Notably,compared to 2,1 exhibits a higher scintillation light yield of 14832 photons MeV^(-1),exceeding that of the commercial scintillator Bi_(4)Ge_(3)O_(12)(8000 photons MeV^(-1)),and a low X-ray detection limit of 22.49 nGy s^(-1),far below the typical diagnostic dose(5.5μGy s^(-1)).Furthermore,scintillating film fabricated by 1 achieves X-ray imaging with a high spatial resolution of 16 lp/mm.The reversible structural interconversion enables solvent-responsive luminescent switches,and thus,the dynamic encryption system capable of multistage decryption was developed.This work not only offers new insight into solvent-regulated clusters transformations but also provides a promising strategy for developing high-performance copper(I)clusters-based scintillators and stimulus-responsive optical devices.
