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| 1 | Two SbX_(5)-based isostructural polar 1D hybrid antimony halides with tunable broadband emission,nonlinear optics,and semiconductor properties显示文摘Metal halide perovskites based on MX6(M is metal and X is halogen)octahedra have developed into significant materials,extensively used in many fields,such as solid-state lighting,semiconductor,and nonlinear optics.However,the MX_(5)square pyramid-based hybrid metal halides beyond zero-dimensional(0D)polyhedrons and clusters are rarely reported.Herein,we reported two new isostructural hybrid antimony halides,namely(2cepyH)SbCl4(1-Cl)and(2cepyH)SbBr4(2-Br)(2cepy=1-(2-chloroethyl)pyrrolidine),characterized by 1D polar polyanionic chains formed by corner-sharing SbX_(5)tetragonal pyramid units.Upon photoexcitation at 340 nm,1-Cl shows broad,yellow phosphorescence emissions stemming from triplet self-trapped excitons,as proved by its long lifetime(6.85μs)and the temperature dependences of broadband emission.To our knowledge,this should be the first observation on the broadband emissive properties in the 1D hybrid metal halide constructed by MX_(5)tetragonal pyramid units.Moreover,second harmonic generation measurements show that the nonlinear optical properties of 2-Br(∼3.2×KDP)are superior to that of 1-Cl(∼1.8×KDP).Experimental and calculated data indicate that the bandgap of 1-Cl is larger than that of 2-Br and that the polar inorganic moieties determine their band structures.Our work opens up a new way for constructing broadband emission materials with novel polar frameworks. | Zhikai Qi Yali Chen Huizhi Gao Fu-Qiang Zhang Shi-Li Li Xian-Ming Zhang | 2021 | Science China Chemistry2021，64，12： | 1 |
| 2 | (NH_(4))_(3)B_(11)PO_(19)F_(3):a deep-UV nonlinear optical crystal with unique[B_(5)PO_(10)F]_(∞)layers显示文摘Deep-ultraviolet(DUV)nonlinear optical(NLO)crystals that can extend the output range of coherent light below 200 nm are pivotal materials for solid-state lasers.To date,KBe_(2)BO_(3)F_(2)(KBBF)is the only usable crystal that can generate DUV coherent light by direct second harmonic generation(SHG),but the layered growth habit and toxic ingredients limit its application.Herein,we report a new fluoroborophosphate,(NH_(4))_(3)B_(11)PO_(19)F_(3)(ABPF),containing four different functional units:[BO_(3)],[BO_(4)],[BO_(3)F]and[PO_(4)].ABPF exhibits a KBBF-like structure while eliminating the limitations of KBBF crystal.The unique[B_(5)PO_(10)F]_(∞)layers enhance ABPF’s performance;for example,it has a large SHG response(1.2×KDP)and a sufficient birefringence(0.088 at 1064 nm)that enables the shortest phase-matching wavelength to reach the DUV region.Meanwhile,the introduction of strong B-O-P covalent bonds decreases the layered growth habit.These findings will enrich the structural chemistry of fluoroborophosphate and contribute to the discovery of more excellent DUV NLO crystals. | Bingliang Cheng Zijian Li Yu Chu Abudukadi Tudi Miriding Mutailipu Fangfang Zhang Zhihua Yang Shilie Pan | 2022 | National Science Review2022，9，8： | 0 |
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