Novel Polyselenidoarsenate and Selenidoarsenate: Solvothermal Synthesis and Characterization of [Co(phen)₃][As₂Se₂(μ-Se₃)(μ-Se₅)] and [Co(phen)₃]₂[As₈Se₁₄]

Abstract

Novel cobalt polyselenidoarsenate [Co(phen)(3)][As(2)Se(2)(μ-Se(3))(μ-Se(5))] (1; phen = 1,10-phenanthroline) was methanolothermally synthesized by the reaction of CoCl(2), As(2)O(3), and Se templated by phen in a CH(3)OH solvent at 130 °C. The same reaction in a H(2)O solvent yielded cobalt selenidoarsenate [Co(phen)(3)](2)[As(8)Se(14)] (2). In 1, the AsSe(+) units are alternately joined by the μ-Se(3)(2-) and μ-Se(5)(2-) bridging ligands to form a novel helical polyselenidoarsenate chain [As(2)Se(2)(μ-Se(3))(μ-Se(5))(2-)](∞). In 2, eight pyramidal AsSe(3) units are connected via corner sharing into the new member of the selenidoarsenate aggregate [As(8)Se(14)](4-) with a condensation grade of 0.571, which represents the first discrete selenidoarsenate(III) with a condensation grade of above 0.50. The octahedral complex [Co(phen)(3)](2+) is formed in situ to act as a countercation in compounds 1 and 2. 1 and 2 exhibit steep absorption band gaps at 2.09 and 2.16 eV, respectively.

Structural Diversity, Optical and Magnetic Properties of a Series of Manganese Thioarsenates with 1,10-Phenanthroline or 2,2′-Bipyridine Ligands: Using Monodentate Methylamine as an Alkalinity Regulator

“…For 5 , another interesting structural feature is its mixed-valent As III /As V character, which is in good agreement with the bond valence sum calculations As1 = 5.166, As2 = 2.885. The mixed-valent As III /As V character observed here, the +3 valent As in polythioarsenate [As III S(S 5 )] − anion, is quite different from several other chalcogenoarsenates, ,,, where the +3 valent As all exists in pyramidal (As III S 3 ) − ,− or in their self-condensed polymeric anionic species. ,, …”

“…In comparison with traditional aliphatic chelating amines, chelating π-conjugated ligands featuring delocalized electrons over their aromatic rings can confer peculiar photochemical and electrochemical properties on their TM complex cations, which may also have unusual structure directing abilities. , It is very attractive to incorporate unsaturated TM π-conjugated ligand complex cations into inorganic main-group element chalcogenide frameworks to form hybrid chalcogenidometalates; however, studies on this area are limited, especially, the physical property of the target compounds, which is usually not examined in detail. From a synthetic point of view, aliphatic multidentate chelating amines were usually used as an alkalinity regulator in the solvothermal syntheses of π-conjugated ligand-containing chalcogenidometalates; ,− however, their alkalinity regulation ability is impeded by their strong chelating inclination to TM 2+ ions, which will produce byproducts.…”

Solvent effect on condensation of pyramidal [AsSe3]3–: solvothermal syntheses of new selenidoarsenates containing transition metal(II) complexes with 1,10-phenanthroline

“…Unit cell dimensions (Å , ) a 10.3554 (8) 10.3682 (14) 13.1405 (3) 13.0546 (3) b 12.7339 (8) 12.7834 (11) 13.3007 (3) 13.1712 (5) c 17.4755 (17) 17.524 (3) 14.0142 (2) 13.6412 (4) 76.601 (6) 76.444 (12) 60.24 (2) 117.048 (9) 88.083 (7) 87.986 (15) 65.42 (2) 99.380 (10) 66.684 (5) 66.711 (10) 74.20 (2) 105.67 ( [34,35]. During solvothermal reactions, TM ions are coordinated by three phen, forming [TM(phen) 3 ] 2þ cationic counter ions to the selenidoarsenate and polyselenidoarsenate anions, but reaction solvents exert influence on the selenidoarsenate anions.…”

“…Hydro-or solvothermal synthesis from 100-200 C and extraction technique at room temperature have proven to be useful for access to chalcogenidoarsenate [6][7][8][9] [22], [TM(dien) 2 ]As 2 Se 6 (dien ¼ diethylenetriamine) (TM ¼ Co, Ni), and [Mn(dap) 3 ]As 2 Se 6 (dap ¼ 1,2-diaminopropane) [23]. Recently, selenidoarsenates -As 2 Se 4 , -As 2 Se 5 , -As 4 Se 7 , and -As 4 Se 8 were obtained in manganese complexes with the tridentate terpy (terpy ¼ 2,2 0 ;6 0 , 2 00 -terpyridine) or tetradentate tren as the coligands [24][25][26] [34,35] were prepared by reactions of TMCl 2 , As 2 O 3 , Se, and phen under methanol-thermal conditions. Now, the TM/As/Se/phen system is investigated in water and CH 3 OH aqueous solution, and selenidoarsenates(III) [TM(phen) 3 ] 2 [As 8 Se 14 ] (TM ¼ Ni (1), Zn (2)) and polyselenidoarsenates(III) [TM(phen) 3 ][As 2 Se 6 ] (TM ¼ Co (3), Ni (4)) were synthesized and characterized.…”

1-D Selenidoindates {[In2Se5]}∞ Directed by Chiral Metal Complex Cations of 1,10-Phenanthroline

“…However, in most cases, the chalcogenometalate with [M(phen) 3 ] n + cation as template or directing species is a chemically racemic mixture of achiral crystals; namely, both the Δ and Λ configurations coexist in a crystal . Only limited such mechanical racemic mixtures of single enantiomer crystals have been reported until now based on our knowledge …”