Two Organic Hybrid Manganese Selenoarsenates: The Discovery of One-Dimensional Low-Valent Selenoarsenate(II)

Abstract

Two organic hybrid manganese selenoarsenates, [Mn­(en)3]­[MnAsII 2Se4] (1; en = ethanediamine) and {[Mn­(atep)]2[Mn­(tepa)]­(AsVSe4)2} [2; atep = 4-(2-aminoethyl)­triethylenetetramine], were made under mild solvothermal conditions. 1 is a new type of one-dimensional low-valent selenoarsenate­(II) constructed by the linkages of tetrahedral [MnSe4] units and two manners of bridging of [AsII 2Se4]4– anions. 2 comprises a neutral {[Mn­(atep)]2[Mn­(tepa)]­(AsVSe4)2} molecule with a rare seven-coordinated manganese center, which represents the sole example of an organic hybrid selenoarsenate with the [Mn­(tepa)]2+ complex as the bridging group. Both 1 and 2 exhibit special photocurrent responses upon visible-light illumination and magnetic properties.

New types of open-framework vanadium borophosphates with photocatalytic properties

“…4). The average current densities are 40.11 μA cm −2 for 1 , 41.48 μA cm −2 for 2 and 41.23 μA cm −2 for 3 , which are compared with other photoelectric response materials, 58,59 indicating that the photo-induced electron−hole pairs can be better generated and separated. The semiconductor type and flat band potential of 1–3 were tested by the Mott–Schottky method.…”

Rare examples of hybrid chalcogenoarsenate(iii) incorporating trivalent vanadium complexes

“…The chalcophilic TM ions (such as Cu, Ag, and Hg) can bond directly to the chalcogen (Q = S and Se) atoms of chalcogenoarsenate anions via TM–Q bonds, 7 while other TM ions can easily form either saturated or unsaturated TM complexes with organic amines. The saturated TM complexes (TM = Mn, Fe, Co, and Ni) serve as structure-directing agents, space fillers and charge compensating ions in chalcogenoarsenates, 7 a ,8 and the unsaturated TM complexes are able to further interact with chalcogenoarsenate anions, 9 resulting in new organic hybrid chalcogenoarsenates with varied structures, as exemplified by [{Mn(tren)} 2 (μ-As 2 Se 5 )] 9 c [Mn(tren)As 4 Se 7 ], 9 d [Mn(dien) 2 ][Mn(dien)AsS 4 ] 2 ·4H 2 O, 9 i [Mn-(en) 3 ] 2 [Mn(en) 2 AsS 4 ][As 3 S 6 ], 9 i and {[Mn(atep)] 2 [Mn(tepa)]-(AsSe 4 ) 2 }. 9 l Similar organic hybrid chalcoantimonate( iii ) containing transition metal complexes (TM = Cr 3+ , Mn 2+ , Fe 2+ , Co 2+ , Ni 2+ , and Zn 2+ ) 10 have also emerged, and TM ions are relatively stable in an aqueous solution of organic amine or organic amine solution.…”

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

“…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. Such as [As 2 Q 4 ] 2- ( Smith et al, 1996 ; Xu et al, 2021 ), [As 2 Se 5 ] 4- ( Fu et al, 2006 ; Jia et al, 2006 ; Chen et al, 2021 ), [As 2 Se 6 ] 2- ( Wendel and Müller, 1995 ; Smith et al, 1998 ; Fu et al, 2005b ; Jia et al, 2011 ; Zhao et al, 2011b ; Yang et al, 2018 ), [As 3 Q 6 ] 3- ( An et al, 2017 ; Fu et al, 2005a ; Zhou et al, 2017 ), [As 4 Q 6 ] 2- ( Ansari et al, 1992 ; Smith et al, 1996 ), [As 4 S 7 ] 2- ( Vater and Sheldrick, 1997 ), [As 4 Q 8 ] 4- ( Kromm and Sheldrick, 2008 ), [As 6 S 10 ] 2- ( Vater and Sheldrick, 1997 ), [As 8 S 13 ] 2- ( Sheldrick and Kaub, 1985b ; Sheldrick and Kaub, 1985a ; Vater and Sheldrick, 1998 ), [As 10 Q 3 ] 2- ( Smith et al, 1996 ). The thiophilic metal ions (Cu + , Ag + , Cd 2+ , Hg 2+ ), which have less or little tendency to form complex cations with the strongly chelating amines, usually bond directly to the chalcogen elements.…”