Novel One-, Two-, and Three-Dimensional Selenidostannates Templated by Iron(II) Complex Cation

Abstract

The novel iron selenidostannates [Fe(bipy)₃]Sn₄Se₉·2H₂O (1) and [Fe(bipy)₃]₂[Sn₃Se₇]₂·bipy·2H₂O (2) (bipy = bipyridine) were prepared by the reactions of Sn, Se, FeCl₂·4H₂O, bipy, and dien with/without KSCN under hydrothermal conditions (dien = diethylenetriamine). In 1, four SnSe₅ units condense via edge sharing to form the novel 3-D framework selenidostannate (∞)³[Sn₄Se₉²⁻] containing an interpenetrating channel system. The [Fe(bipy)₃]²⁺ cations are accommodated in the different channels according to the conformation of the [Fe(bipy)₃]²⁺ cation. In 2, three SnSe₅ units share edges to form a 2-D (∞)²[Sn₃Se₇²⁻] layered anion, while two SnSe₅ units and one SnSe₄ unit are connected via edge sharing, forming a 1-D (∞)¹[Sn₃Se₇²⁻] chainlike anion. The (∞)¹[Sn₃Se₇²⁻], [Fe(bipy)₃]²⁺, bipy, and H₂O species are embedded between the (∞)²[Sn₃Se₇²⁻] layers. 2 is the first example of a selenidostannate constructed by both (∞)²[Sn₃Se₇²⁻]and (∞)¹[Sn₃Se₇²⁻] anions. The coexistence of 1-D (∞)¹[Sn₃Se₇²⁻] and 2-D (∞)²[Sn₃Se₇²⁻] anions in 2 might support the possible reaction mechanism that the (∞)²[Sn₃Se₇²⁻] anions are formed by condensation of the (∞)¹[Sn₃Se₇²⁻] chains. 1 and 2 exhibit band gaps at 1.43 and 2.01 eV, respectively.

Synthesizing 2D and 3D Selenidostannates in Ionic Liquids: The Synergistic Structure‐Directing Effects of Ionic Liquids and Metal–Amine Complexes

“…Compound 3 belongs to the Pn space group. Interestingly,t he asymmetric unit of 3 consists of two isolated [Ni(tepa)Cl] + MAC, four [Bmmim] + cations, one anionic [Sn 12 Se 28 ] 8À unit, and one [Ni(tepa)] 2 + complex that decorates the [Sn 12 Se 28 ] 8À unit through ad irect Ni···Se bond. In 3,t he Ni atoms are all in octahedral coordination geometry.The coordination sphere of the Ni 2 + ion of the isolated [Ni(tepa)Cl] + is fulfilledb yf ive Na toms from ap entadentate tepa molecule and aC la tom ( Figure 3a).…”

“…Compound 4 crystallizes in the trigonal R3 c space group and features a3 Do pen-framework structure with the formula (Bmmim) 2 [Ni(1,2-pda) 3 ]Sn 8 Se 18 .T he asymmetricu nit of 4 is composed of one [Ni(1,2-pda) 3 ] 2 + MAC (Figure 4a ( Figure S4), which generates two chiral channel systemsc ircumscribed by helical chains with left-handed ( Figure 4c,l eft; denoted L-channel,i nb lue) and right-handed( Figure4c, right; denoted R-channel, in green) configurations. As ar esult, each [Sn 12 Se 33 ]r ing unit is alternately surrounded by three L-channels and three R-channels, and each L-or R-channel is surrounded by three [Sn 12 Se 33 ]r ing units. For the L-and R-channels, ac ross-sectional diameter of approximately 8.3 c an be observed.…”

“…Figure 4d showst he perspective views of 4 towards the (001), (02 1), and (1 01) Se 20 ]( Bmim = 1-butyl-3-methylimidazolium), [3a, 5b] 3D-[Bmmim] 4 [Sn 9 Se 19 (Se 2 ) 0.9 Se 0.1 ], [3a] 3D-[Prmmim] 4 [Sn 9 Se 19 (Se 2 ) 0.93 Se 0.07 ]( Prmmim = 1-propyl-2,3-dimethylimidazolium), [3a] 3D-[Bmmim] 8 [Sn 18 Se 40 ], [11] and 3D-[Fe(bipy) 3 ]Sn 4 Se 9 ·2H 2 O( bipy = 2,2'-bipyridyl), [12] which contain either an IL cation or am etal-complex cation as the SDA and counterion,w hereas in 4 the synergistic effecto ft he MAC and IL cations results in ad istinct 3D anionic framework of the selenidostannate. Note that the framework of 3D-[Sn 4 Se 9 ] n 2nÀ in 4 is entirely different from that of 2D-[Sn 4 S 9 ] n 2nÀ [13] and that of 3D-[Fe(bipy) 3 ]Sn 4 Se 9 ·2H 2 O, in which the [Sn 12 Se 33 ]S BUs are connectedt hrough asymmetric [Sn 4 Se 13 ]u nits ( Figure S4) to form a3 Df ramework. [12] To our knowledge, 4 represents the first case of a3 Ds elenidostannate with both MAC and IL cations as SDAs and counterions.…”

“…As ac ontinuation of our research, the current work is focused on investigating the synergistic structure-directing effect of ILs and MACs with different polyamines. For this purpose, another three polyamines in addition to ethylenediamine (en) were chosen as ligandst oc onstruct MACs as synergistic SDAs with an imidazolium-basedI L. As ar esult,f our crystalline selenidostannates with different MACs were obtained, namely, 2D-(Bmmim) 3 [Ni(en) 3 ] 2 [Sn 9 Se 21 ]Cl (1,B mmim = 1-butyl-2,3-dimethyl-imidazolium), 2D-(Bmmim) 8 [Ni 2 (teta) 2 (m-teta)]Sn 18 Se 42 (2,t eta = triethylenetetramine), 2D-(Bmmim) 4 [Ni(tepa)Cl] 2 -[Ni(tepa)Sn 12 Se 28 ]( 3,t epa = tetraethylenepentamine), and 3D-(Bmmim) 2 [Ni(1,2-pda) 3 ]Sn 8 Se 18 (4,1 ,2-pda = 1,2-diaminopropane). Remarkably,t he anionic structures of 1-4 show variations from distinct 2D layers of [Sn 3 Se 7 ] n 2nÀ in 1 and 2 and a2 D layer of [Ni(tepa)Sn 12 Se 28 ] n 6nÀ in 3 to a3 Do penf ramework of [Sn 4 Se 9 ] n 2nÀ in 4.T he asymmetric eight-membered ring in 2 and the framework in 4 were discovered for the first time.…”

The Two‐Dimensional Anion [Sb6Se10]2–: Solvothermal Synthesis, Crystal Structure, and Properties of an Iron ­Selenidoantimonate(III) [Fe(phen)3]Sb6Se10

“…A solvent is necessary in the syntheses of ternary TM ‐chalcogenidometallate using aromatic amines instead of the liquid ethylene polyamines as the coordinative ligands. The composition and nature of the solvent play crucial roles in these preparation 34–36…”