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

Abstract

Two 1-D selenidoindates {[M(phen)(3)]In(2)Se(5)·H(2)O}(n) (M = Ni, Fe) were synthesized by a solvothermal method. The 1-D {[In(2)Se(5)](2-)}(n) anion is a new type of single 1-D structure constituted by an alternately fused four-membered In(2)Se(2) ring and five-membered In(2)Se(3) ring. The chalcogenoindates were separated as mechanical racemic mixtures of single enantiomer crystals, in which the R-helix of 1-D InSe anion is directed by the related clockwise (Δ) cations of [M(phen)(3)](2+) or the L-helix of 1-D anion is directed by the related anticlockwise (Λ) cation. The π···π, C···Se, and C-H···Se oriented interactions of metal complex cations with selenidoindate anions play an important role in the formation of the chiral crystals. The embedded [M(phen)(3)](2+) cations improve the optical absorption of the 1-D semiconductor materials.

Solvothermal Synthesis of One‐dimensional Chalcogenides Containing Group 13 Elements

“…Compound 2 is also isostructural to our recently reported [C 6 H 16 N 2 ][In 2 Se 3 (Se 2 )],16 and similar [In 2 Se 3 (Se 2 )] 2– chains have been subsequently found in {[M(phen) 3 ] · In 2 Se 5 · H 2 O} n 24 and [Mn(en) 3 ][In 2 Se 5 ] 25. The selenium‐selenium distance in the (Se 2 ) 2– perselenide unit of 2 (2.3702(8) Å) is comparable to those in previously described [M 2 Se 3 (Se 2 )] 2– (M = In, Ga) chains 11,16,24,25…”

“…A [CdSnTe 4 ] 2– chain, formed by alternating edge‐ and corner‐linked tetrahedra, and in which cadmium and tin atoms are ordered, has also been described 30. The [M 2 Se 3 (Se 2 )] 2– chain found in 2 – 5 was reported for the first time very recently,16 and to the best of our knowledge, all known examples of this kind of chain contain a single metal 11,24,25. The materials described here therefore represent the first example of ternary mixed‐metal [M 2 Se 3 (Se 2 )] 2– chains.…”

“…This material contains [GaS 3 ] – chains, consisting exclusively of five‐membered [Ga 2 S 3 ] rings. By contrast, recent literature reports suggest that incorporation of (Q 2 ) 2– units, as well as larger (Q n ) 2– units, into materials produced under solvothermal conditions, occurs more readily in selenides 11,16,24,25. An even greater tendency for the formation of chalcogen‐rich phases, containing chalcogen–chalcogen bonds, is found for the heavier congener, tellurium.…”

Synthesis and Structural Characterization of Cs2Ga2Se5

“…Analogous 1 ∞ [ M 2 Se 3 (Se 2 ) 2– ] chains have been recently reported for [C 6 H 16 N 2 ][In 2 Se 3 (Se 2 )],10 [ M (C 12 H 8 N 2 ) 3 ][In 2 Se 3 (Se 2 )]H 2 O ( M = Ni, Fe),11 [C 4 H 14 N 2 ][Ga 2 Se 3 (Se 2 )],12 [C 6 H 16 N 2 ][Ga 2 Se 3 (Se 2 )],13 and [Mn(C 2 H 8 N 2 ) 3 ][In 2 Se 3 (Se 2 )] 14. Cs 2 Ga 2 Se 5 however represents the first example for a gallium polyselenide 1 ∞ [Ga 2 Se 3 (Se 2 ) 2– ] with alkali metal counterions.…”

“…The title compound as well as the recently reported Cs 2 Ga 2 S 5 9 are the first examples of anionic chains 1 ∞ [ M 2 Q 3 ( Q 2 ) 2– ] ( M = Al, Ga, In; Q = S, Se, Te) among group 13 chalcogenometallates containing alkali metal cations. Analogous 1 ∞ [ M 2 Q 3 (Q 2 ) 2– ] chains have been reported in [C 6 H 16 N 2 ][In 2 Se 3 (Se 2 )],10 [ M (C 12 H 8 N 2 ) 3 ][In 2 Se 3 (Se 2 )]H 2 O ( M = Ni, Fe),11 [C 4 H 14 N 2 ][Ga 2 Se 3 (Se 2 )],12 [C 6 H 16 N 2 ][Ga 2 Se 3 (Se 2 )],13 and [Mn(C 2 H 8 N 2 ) 3 ][In 2 Se 3 (Se 2 )],14 using organic cations as structure directing agents.…”