The introduction of oxofluoride anion into anionic group assists to tune optical properties owing to the change of coordination,electronegativity,and according anionic framework.Here,we proposed a rational design of n...The introduction of oxofluoride anion into anionic group assists to tune optical properties owing to the change of coordination,electronegativity,and according anionic framework.Here,we proposed a rational design of new compounds by fluorine-driven structure and optical property evolution.A new borophosphate Ba_(2)BP_(3)O_(11)with the monoclinic space group P2_(1/c) has been synthesized in the sealed system.Ba_(2)BP_(3)O_(11)exhibits a rare P-O-P bridge formation,which is the first example in alkaline-earth metal borophosphates.By further substituting[BO_(4)]^(3-)with[BO_(3)F]^(4-),the first alkaline-earth metal/lead fluoroborophosphates M_(2)BP_(2)O_(8)F(M=Ba and Pb)with the same space group were designed.Since the scissors effect of fluorine,in M_(2)BP_(2)O_(8)F(M=Ba and Pb),a BO_(3)F tetrahedron corner-sharing with three PO_(4)tetrahedra forms 1D chains along the b-axial direction,which are filled by MO_(n)(M=Ba/Pb,n=5,6,8)distorted polyhedra.The first principles calculation shows that the borophosphate Ba_(2)BP_(3)O_(11)has a birefringence about 0.013@1,064 nm,while the fluoroborophosphates M_(2)BP_(2)O_(8)F(M=Ba and Pb)have the values of 0.035 and 0.043@1,064 nm,respectively.Such an apparent enhancement in birefringence is derived from synergies of the oxyfluoride and cation.The introduction of fluorine-containing heteroanionic groups provides a feasible strategy to design novel promising optical materials.展开更多
基金supported by the National Natural Science Foundation of China(51972336,61835014,51922014)the International Partnership Program of CAS(1A1365KYSB20200008)+4 种基金the Instrument Developing Project of CAS(GJJSTD20200007)the Science and Technology Service Network Initiative of CAS(KFJ-STS-QYZD-130)Basic Frontier Science Research Program of CAS(ZDBS-LY-SLH035)the Western Light Foundation of CAS(Y92S191301)Fujian Institute of Innovation,CAS(FJCXY18010202)。
文摘The introduction of oxofluoride anion into anionic group assists to tune optical properties owing to the change of coordination,electronegativity,and according anionic framework.Here,we proposed a rational design of new compounds by fluorine-driven structure and optical property evolution.A new borophosphate Ba_(2)BP_(3)O_(11)with the monoclinic space group P2_(1/c) has been synthesized in the sealed system.Ba_(2)BP_(3)O_(11)exhibits a rare P-O-P bridge formation,which is the first example in alkaline-earth metal borophosphates.By further substituting[BO_(4)]^(3-)with[BO_(3)F]^(4-),the first alkaline-earth metal/lead fluoroborophosphates M_(2)BP_(2)O_(8)F(M=Ba and Pb)with the same space group were designed.Since the scissors effect of fluorine,in M_(2)BP_(2)O_(8)F(M=Ba and Pb),a BO_(3)F tetrahedron corner-sharing with three PO_(4)tetrahedra forms 1D chains along the b-axial direction,which are filled by MO_(n)(M=Ba/Pb,n=5,6,8)distorted polyhedra.The first principles calculation shows that the borophosphate Ba_(2)BP_(3)O_(11)has a birefringence about 0.013@1,064 nm,while the fluoroborophosphates M_(2)BP_(2)O_(8)F(M=Ba and Pb)have the values of 0.035 and 0.043@1,064 nm,respectively.Such an apparent enhancement in birefringence is derived from synergies of the oxyfluoride and cation.The introduction of fluorine-containing heteroanionic groups provides a feasible strategy to design novel promising optical materials.
