Solvothermal Synthesis and Characterization of a Series of Lanthanide Thiostannates(IV): The First Examples of Inorganic–Organic Hybrid Cationic Lanthanide Thiostannates(IV)

Abstract

A series of new lanthanide thiostannates(IV), [Y(2)(dien)(4)(μ-OH)(2)]Sn(2)S(6) (1, dien = diethyl-enetriamine), (tetaH)(2)[Ln(2)(teta)(2)(tren)(2)(μ-Sn(2)S(6))]Sn(2)S(6) [Ln = Eu (2), Sm (3); teta = triethylenetetramine; tren = tris(2-aminoethyl)amine] and [Eu(2)(tepa)(2)(μ-OH)(2)(μ-Sn(2)S(6))](tepa)(0.5)·H(2)O (4, tepa = tetraethylene-pentamine) were solvothermally synthesized and structurally characterized. 1 consists of a binuclear [Y(2)(dien)(4)(μ(2)-OH)(2)](4+) cation and a discrete dimeric [Sn(2)S(6)](4-) anion. Both 2 and 3 are isostructural and composed of [Ln(2)(teta)(2)(tren)(2)(μ-Sn(2)S(6))](2+) cations, protonated triethylenetetramines (tetaH), and discrete dimeric [Sn(2)S(6)](4-) anions. A Sn(2)S(6)(4-) anion bridges two [Ln(teta)(tren)](3+) cations via the trans-S(t) (t = terminal) atoms to form the first examples of inorganic-organic hybrid thiostannate cations [Ln(2)(teta)(2)(tren)(2)(μ-Sn(2)S(6))](2+). 4 consists of one-dimensional (1-D) neutral chains [Eu(2)(tepa)(2)(μ-OH)(2)(μ-Sn(2)S(6))](n) built up from the linkage of dinuclear complex cations [Eu(2)(tepa)(2)(μ(2)-OH)(2)](4+) and bridging anions [Sn(2)S(6)](4-), free tepa molecules, and lattice water molecules. The present compounds exhibit wide-band gap semiconducting properties with absorption band edges between 2.40 and 2.91 eV.

Transition Metal Complexes with Linkage to the Thiostannate Units Forced by Suitable Amine Molecules

“…The charge compensation in these compounds can be achieved in different ways: (a) inorganic cations, (b) inorganic‐organic hybrid compounds with protonated amine molecules as counterions, (c) compounds with integrated transition metal ions (TM) in the thiostannate unit and protonated amines as counterions, and finally (d) compounds containing [TM(amine) n ] m + or [ Ln (amine) n ] m + complexes for charge compensation as summarized in several review articles , , . In the latter group mainly the [Sn 2 S 6 ] 4– unit is observed, whereas the [SnS 4 ] 4– anion is less common , , , . Other thiostannate ions like for example [Sn 3 S 7 ] 2– , [Sn 4 S 9 ] 2– ,, [Sn 5 S 12 ] 4– , [Sn 3 S 9 ] 6– , or [Sn 4 S 10 ] 4– are only found in pure inorganic or inorganic‐organic hybrid compounds so far.…”

Solvothermal Syntheses and Characterization of a Series of New Selenidostannates with Lanthanide Complexes as Counterions

“…The lamp was kept on continuously, and a manual shutter was used to block exposure of the sample to the light. The sample was typically irradiated at intervals of 60 s. (6) 10.2401 (14) 10.2141 (13) 10.2038 (17) b (Å ) 14.1276 (9) 14.1163 (19) 14.1184 (18) 14.176 (3) c (Å ) 18.0682 (11) 18.030 (3) 18.000 (2) 18.041 (3) b (°)…”

“…Compared with the overwhelming chalcogenido-stannates containing TMCs, lanthanoid chalcogenidostannates are less explored under mild solvothermal conditions [14][15][16], mainly because they are comparatively unstable with respect to heat, water, oxygen, and light [17]. More recently, we have attempted the preparation of lanthanoid chalcogenidostannates in chelating amine solutions by the solvothermal methods, and prepared a series of lanthanoid chalcogenidostannates containing [Sn 2 Q 6 ] 4-anions [Y 2 (dien) 4 (l-OH) 2 ]Sn 2 S 6 [18], (tetaH) 2 [Ln 2 (teta) 2 (tren) 2 (l-Sn 2 S 6 )]Sn 2 S 6 (Ln = Eu, Sm) [18], [Eu 2 (tepa) 2 (l-OH) 2 (l-Sn 2 S 6 )]-(tepa) 0. 5 …”

A New Solvothermal Synthetic Route Yields the New Thio­stannate [La(dien)3]2[Sn2S6]Cl2

“…(NH 4 ) 2 Ag 6 Sn 3 S 10 ,13 [{Mn(en) 2 } 2 (μ‐en)(μ‐Sn 2 S 6 )] x ,14 (enH 2 )HgSnS 4 ,15 (DBUH)CuSnS 3 16 (DBU = 1,8‐diazabicyclo[5.4.0]undec‐7‐ene), (1,4‐dabH 2 ) M 2 SnS 4 ( M = Cu,16 Ag,17 1,4‐dab = 1,4‐diaminobutane), (DBNH) 2 Cu 6 Sn 2 S 8 18 (DBN = 1,5‐diazabicyclo[4.3.0]non‐5‐ene), (1,4‐dabH) 2 MnSnS 4 ,19 [Mn(1,2‐dach) 2 ]Sn 2 S 6 · 2(1,2‐dach)20 (1,2‐dach = 1,2‐diaminocyclohexane), (dienH 2 )Cu 2 Sn 2 S 6 ,21 or [Co 2 (cyclam) 2 Sn 2 S 6 ] · 2H 2 O22 (cyclam = 1,4,8,11‐tetraazacyclotetradecane). Expanding the emerging field of possible applications of thiostannates or tin‐sulfur compounds as sensors or absorbers, ion exchangers catalysts,23 capping molecules of colloidal particles24 or for the generation of mesostructured sulfides25 may be achieved by applying rare earth elements as further constituents 26–28…”

“…For these reasons Ln 3+ containing thiostannates are difficult to synthesize under such reaction conditions. Nevertheless, some compounds were prepared following the solvothermal approach like [Nd(dien) 3 ] 2 [(Sn 2 S 6 )Cl 2 ],27 [Y 2 (dien) 4 (μ‐OH) 2 ]Sn 2 S 6 ,28 [Sm 2 (en) 6 (OH) 2 ]Sn 2 S 6 , [Sm(dien) 3 ] 2 (Sn 2 S 6 )(SH) 2 ], and [Sm(dien) 3 ] 2 [(Sn 2 S 6 )Cl 2 ]31 or [{Eu(en) 3 } 2 (μ‐OH) 2 ]Sn 2 S 6 32, to name just a few 33. These compounds were prepared by using amine molecules and elemental sulfur as starting materials for the generation of sulfide anions to form the thiostannate anion.…”