Wide transmittance range is an essential factor for the design of infrared optical materials.Traditionally,the designs of mid-far infrared crystals have focused on oxygenfree systems of chalcogenides and pnictides.Nev...Wide transmittance range is an essential factor for the design of infrared optical materials.Traditionally,the designs of mid-far infrared crystals have focused on oxygenfree systems of chalcogenides and pnictides.Nevertheless,the introduction of elements with large atomic numbers,such as the lone-pair cation Pb^(2+) and halogen anion I^(-),based on the oxyhalides,can broaden the infrared transmittance range.Thus,two new polymorphs of Pb(Ⅱ)-containing oxyhalides,Pb_(14)O_(8)I_(12)(α-POI)and Pb_(7)O_(4)I_(6)(β-POI),are successfully synthesized via the high-temperature solution method.Interestingly,they crystallize in the same space group,P1,and present unprecedented[O_(8)Pb_(14)]clusters from the perspective of oxocentered[OPb_(4)]basic units.Remarkably,POI exhibits a quite wide transparent range(0.47-16.0μm),which enlightens the oxyhalides with prominent infrared optical properties.Additionally,the first principles calculations show that they have large birefringence(0.139 and 0.108 for α-and β-POI at 1064 nm,respectively),which makes POI promising infrared optical materials.展开更多
基金supported by the Youth Innovation Promotion Association of Chinese Academy of Sciences(CAS)(2020429)the National Natural Science Foundation of China(22122509,52002398 and 11774414)+3 种基金the West Light Foundation of the CAS(2019-YDYLTD-002)the International Partnership Program of CAS(1A1365KYSB20200008)the Instrument Developing Project of CAS(GJJSTD20200007)the Science and Technology Service Network Initiative of CAS(KFJ-STS-QYZD-130)。
文摘Wide transmittance range is an essential factor for the design of infrared optical materials.Traditionally,the designs of mid-far infrared crystals have focused on oxygenfree systems of chalcogenides and pnictides.Nevertheless,the introduction of elements with large atomic numbers,such as the lone-pair cation Pb^(2+) and halogen anion I^(-),based on the oxyhalides,can broaden the infrared transmittance range.Thus,two new polymorphs of Pb(Ⅱ)-containing oxyhalides,Pb_(14)O_(8)I_(12)(α-POI)and Pb_(7)O_(4)I_(6)(β-POI),are successfully synthesized via the high-temperature solution method.Interestingly,they crystallize in the same space group,P1,and present unprecedented[O_(8)Pb_(14)]clusters from the perspective of oxocentered[OPb_(4)]basic units.Remarkably,POI exhibits a quite wide transparent range(0.47-16.0μm),which enlightens the oxyhalides with prominent infrared optical properties.Additionally,the first principles calculations show that they have large birefringence(0.139 and 0.108 for α-and β-POI at 1064 nm,respectively),which makes POI promising infrared optical materials.
