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![[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst](/_next/image?url=https%3A%2F%2Fcloudfront.jove.com%2FCDNSource%2Fteasers%2F59739.jpg&w=3840&q=50)
[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
Three-dimensional lanthanide(III)-copper(II) compounds based on an unsymmetrical 2-pyridylphosphonate ligand: an
Yun-Sheng Ma1, Hui Li, Jun-Jie Wang
1State Key Laboratory of Coordination Chemistry, Coordination Chemistry Institute, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210093, P. R. China.
Abstract:
Based on an unsymmetrical 2-pyridylphosphonate ligand, two types of Ln(III)-Cu(II) compounds with three-dimensional structures were obtained under hydrothermal conditions, namely, Ln(2)Cu(3)(C(5)H(4)NPO(3))(6).4H(2)O (1.Ln; Ln=La, Ce, Pr, Nd) and Ln(2)Cu(3)(C(5)H(4)NPO(3))(6) (2.Ln; Ln=Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho). Compounds 1.Ln are isostructural and crystallize in chiral cubic space group I2(1)3. In these structures, each Ln ion is nine-coordinate and has a tricapped triprismatic geometry, while each Cu center is six-coordinate with an octahedral environment. The {LnO(9)} polyhedra and {CuN(2)O(4)} octahedra are connected by edge sharing to form an inorganic open framework structure with a 3-connected 10-gon (10,3) topology in which the Ln and Cu atoms are alternately linked by the phosphonate oxygen atoms. Compounds 2.Ln are isostructural and crystallize in trigonal space group R3. In these structures, the {LnO(6)} octahedra are triply bridged by the {CPO(3)} tetrahedra by corner sharing to form an infinite chain along the c axis. Each chain is connected to its six equivalents through corner sharing of {CPO(3)} tetrahedra and {CuN(2)O(2)} planes to form a three-dimensional framework structure in which the Ln and Cu atoms are linked purely by O-P-O units. The formation of these two types of structures is rationalized by quantum chemical calculations, which showed that both the lanthanide contraction and the electron configuration of Cu(II) play important roles. When Cu(II) was replaced by Zn(II), only the first type of compounds resulted. The magnetic properties of complexes 1.Ln and 2.Ln were investigated. The nature of Ln(III)-Cu(II) (Ln=Ce, Pr, Nd) interactions is illustrated by comparison with their Ln(III)-Zn(II) analogues.
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