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New borophosphates Li3Cs2M2B3P6O24 (M = Pb, Sr) have been synthesized by high-temperature solid-state reactions. The single-crystal X-ray diffraction data reveal their non-centrosymmetric cubic space group P213 and lattice parameters of a = 12.7246(3) Å and 12.687(2) Å and V = 2060.31(8) Å3 and 2042.3(4) Å3 for Li3Cs2Pb2B3P6O24 and Li3Cs2Sr2B3P6O24, respectively. They are three-dimensional (3D) [BP2O8]3−∞ anionic frameworks formed by a new double six-membered ring building unit consisting of BO4 and PO4 units joined alternately. Interestingly, such a double six-membered ring is regarded as the structural variation of the 12-membered ring in the known KSrBP2O8, fusing at the BO4 tetrahedron induced by the coexistence of the Li+ and Cs+ cations with their large size difference. The title compounds show weak SHG intensity and exhibit photoluminescence emissions at 410 nm for Li3Cs2Pb2B3P6O24 and 440 nm for Li3Cs2Sr2B3P6O24. [ABSTRACT FROM AUTHOR]

New borophosphates Li3Cs2M2B3P6O24 (M = Pb, Sr) have been synthesized by high-temperature solid-state reactions. The single-crystal X-ray diffraction data reveal their non-centrosymmetric cubic space group P213 and lattice parameters of a = 12.7246(3) Å and 12.687(2) Å and V = 2060.31(8) Å3 and 2042.3(4) Å3 for Li3Cs2Pb2B3P6O24 and Li3Cs2Sr2B3P6O24, respectively. They are three-dimensional (3D) [BP2O8]3−∞ anionic frameworks formed by a new double six-membered ring building unit consisting of BO4 and PO4 units joined alternately. Interestingly, such a double six-membered ring is regarded as the structural variation of the 12-membered ring in the known KSrBP2O8, fusing at the BO4 tetrahedron induced by the coexistence of the Li+ and Cs+ cations with their large size difference. The title compounds show weak SHG intensity and exhibit photoluminescence emissions at 410 nm for Li3Cs2Pb2B3P6O24 and 440 nm for Li3Cs2Sr2B3P6O24. [ABSTRACT FROM AUTHOR]