Copper‐Rich Framework Selenoarsenates Based on Icosahedral Cu₈Se₁₃ Clusters

Abstract

Abstract. Three copper-rich framework selenoarsenates, (H 2 en) 1.5 -[Cu 8 (μ 8 -Se)(AsSe 4 ) 6/2 ] (1), (H 2 dap) 1.5 [Cu 8 (μ 8 -Se)(AsSe 4 ) 6/2 ] (2), and Na 2 (H 2 dap) 0.5 [Cu 8 (μ 8 -Se)(AsSe 4 ) 6/2 ] (3), were synthesized under solvothermal conditions. These three compounds are isostructural and contain a 3D Cu-As-Se framework constructed from novel icosahedral Cu 8 Se 13 clusters linked by As 5+ , with counterions located in the cavi-

Strong Photocurrent Response of Selenoarsenates With Different Transition Metal Complexes as Structure-Directing Agents

“…The wide variety of structures and properties of chalcogenidoarsenates have led to great interest in many areas, including semiconductors, photoelectricity, magnetism, ion exchange, and nonlinear optics ( Sheldrick and Wachhold, 1998 ; Zhou et al, 2009 ; Zhang et al, 2012 ; Xiong et al, 2013 ; Yao et al, 2013 ; Liu et al, 2014 ; Zhou et al, 2015 ; Zhou, 2016 ; An et al, 2017 ; Wang et al, 2020 ; Chen et al, 2021 ; Li et al, 2021 ; Liu et al, 2021 ). The chalcogenidoarsenates are formed by corner- or edge-sharing of [AsQ 3 ] 3- and [AsQ 4 ] 3- (Q = S, Se) units, resulting in a variety of chalcogenidoarsenate aggregates.…”

“…The [AgAs 2 Se 5 ] n 3- chains consist of ψ -bitetrahedral [As 2 Se 5 ] 4- units and tetrahedral coordinated Ag + ions ( Wachhold and Kanatzidis, 1999 ). The three-dimensional [Cu 8 ( μ 8 -Se) (AsSe 4 ) 6/2 ] n 3- framework is constructed of icosahedral Cu 8 Se 13 clusters linked by As 5+ , with counterions located in the cavities ( Zhang et al, 2012 ). The [CdAs 2 Se 4 ] n 2- chain synthesized by our group is made up of a tetrahedral [CdSe 4 ] connected to a dimer As 2 4+ through an As-Se bond, whereas the [HgAs 2 Se 4 ] n 2- chain is formed by of a tetrahedral [HgSe 4 ] connected to a dimer As 2 4+ dimer ( Du et al, 2019 ; Teri et al, 2021b ).…”

The solvothermal synthesis and characterization of quaternary arsenic chalcogenides CsTMAsQ3 (TM = Hg, Cd; Q = S, Se) using Cs+ as a structure directing agent: from 1D anionic chains to 2D anionic layers

“…1, 9 During the past few decades, owing to the diversity of the bonding modes of the chalcogen atoms, the stereochemical effect of the lone electron pairs and the various coordination orientations of As/Sb(III) by sulfur/ selenium atoms, large structural and compositional diversities have been observed for multinary chalcogenides, and therefore a large number of metal chalcogenides compounds have been prepared. Recently, it has been reported that in the combination of the structural units of As x Q y (Q ¼ S, Se) the As III ions tend to adopt the diverse AsQ n (Q ¼ S, Se) (n ¼ 3-6) ligands that can share corners and/or edges with transition metal ions (TM ¼ Ag + , Cu 2+ , Mn 2+ ), 11,[13][14][15][16][17][18][19][20][21][22][23][24] and could form interesting structural various multinary chalcogenides, 8 such as 1D chains, 2D layers, 3D framework. For example, RbAg 2 As 3 Se 6 , 10 NaAg 2 AsS 3 $H 2 O, 13 (NH 3 CH 2 CH 2 NH 3 )AgAsS 4 , 14 CsAgAs 2 Se 4 , 15 27 From the above instances we can see clearly that it is relatively rare for alkali metals cations used as structural directing agents to contain Hg/Cd arsenic chalcogenides in the M-TM-As-Q (M ¼ alkali metals; TM ¼ Hg, Cd; Q ¼ S, Se) systems.…”

A novel copper-rich open-framework chalcogenide constructed from octahedral Cu4Se6 and icosahedral Cu8Se13 nanoclusters

“…The central Se 2À ion bonded to eight tetrahedrally coordinated Cu + ions has a bond valence sum of 2+, which satisfies Pauling's electrostatic valence rule. Such kind of cluster already existed in the Cu-As-Se and [Fe(NH 3 ) 6 ]Cu 8 Sb 3 S 13 frameworks, 17,19 which is different from a hollow structure with the planar trigonal coordination of Cu + , such as K 4 Cu 8 Ge 3 S 12 , 18 (H 2 en) 2 Cu 8 Sn 3 S 12 , 21 and (trenH 3 )Cu 7 Sn 4 S 12 . 22 In the structure of the Cu 4 Se 6 cluster, Cu + is planar trigonally coordinated with three Se 2À ions.…”

“…18 An et al reported the first case of copper-rich selenides with the Cu-As-Se framework. 19 A common feature of these compounds is hollowed Cu 8 S 12 or core-stuffed Cu 8 S 13 /Cu 8 Se 13 icosahedral clusters as SBUs (secondary building units). No other type of cluster co-exists in those open frameworks based on the icosahedral cluster.…”