Synthesis and Structures of Dimanganese(II) Complexes with Spirotricyclic [Mn(μ‐Ge₂Se₇)Mn] and [Mn(μ‐Sn₂Se₆)Mn] Cores

Abstract

Solvothermal reaction of [MnCl 2 (cyclam)]Cl with GeSe 2 at a 1:1 molar ratio in CH 3 OH/H 2 O (1/1) at 150°C affords the dimanganese(II) complex [{Mn(cyclam)} 2 (μ-Ge 2 Se 7 )] · CH 3 OH · 1.5H 2 O (1) with a spirotricyclic [Mn(μ-Ge 2 Se 7 )Mn] core. The strained four-membered Mn-Se t -Ge-Se t Ј rings (Se t ϭ terminal Se atom) exhibit long Mn-Se t distances in the range 2.725(2)Ϫ2.745(2) Å and narrow average Se t -Mn-Se t Ј angles of 85.87(4)°. The solvothermal reaction of [MnCl 2 (cyclam)]Cl with SnSe and Se leads to formation of the analogous complex [{Mn(cyclam)} 2 (μ-Sn 2 Se 6.15 )] (2), in which bridging [Sn 2 Se 6 ] 4Ϫ and [Sn 2 Se 7 ] 4Ϫ ligands are disordered at a ratio of 85:15. Employment 1005 of [MnCl 2 (terpy)] under similar conditions generates two complexes of the formula [{Mn(terpy)} 2 (μ-Sn 2 Se 6 )] 3 and 4, of which the former also contains a spirotricyclic core, whereas the Se t atoms of the latter coordinate symmetry-related Mn II atoms in a 1-D polymer. The Mn-Se t bond distances of 2.584(1) and 2.549(1) Å in the resulting chair-shaped eight-membered rings of 4 are much shorter than in 1 and 2.

Solvothermal Syntheses, Crystal Structures, and Thermal Properties of the First Example of Selenidostannates with Mixed Ethylene Polyamine‐Coordinated Transition Metal Complexes as Counterions

“…Now, a series of hexachalcogenostannate salts containing transition metal complexes were preparedby solvothermal techniques. The examples include [ M (en) 3 ] 2 Sn 2 S 6 ( M = Mn, Co, Ni, Zn), [10, 11] [ M (en) 3 ] 2 Sn 2 Te 6 ( M = Mn, Zn),12 [Zn(en) 3 ] 2 Sn 2 Te 6 · en13 (en = ethylenediamine), [Ni(dien) 2 ] 2 Sn 2 S 6 11 (dien = diethylenetriamine), [Ni(dap) 3 ] 2 Sn 2 S 6 · 2H 2 O (dap = 1,2‐diaminopropane), [Co(tren)] 2 Sn 2 S 6 , [Ni(tren)] 2 Sn 2 S 6 [tren = tris(2‐aminoethyl)amine],14 [ M (tepa)] 2 Sn 2 S 6 ( M = Fe, Co, Ni) (tepa = tetraethylenepentamine),15 and [{Mn(cyclam)} 2 (μ‐Sn 2 Se 6 )] (cyclam = 1,4,8,11‐tetraazacyclotetradecane) 16…”

Five dimeric thiogermanates with transition metal complexes of multidentate chelating amines: Syntheses, structures, magnetism and photoluminescence

“…Up to now, in the known hybrid chalcogenogermanates, the TMCs are generally used as discrete counter-cations [23][24][25], while the examples of chalcogenogermannates integrated with TMCs via TM-S/Se bonds are limited, such as {[Cr(en) 2 ](GeS 4 )} À , {[Cr(en)] 2 (GeSe 4 ) 2 } 2À [26], {[Mn(cyclam)] 2 (l-Ge 2 Se 7 )}ÁCH 3 OHÁ1.5H 2 O (cyclam = 1,4,8,11-tetraazacyclotetradecane) [27], {[Co(tepa)] 2 (l-Ge 2 S 6 )}, {[M(tepa)] 2 (lGe 2 Se 6 )} (M = Mn, Fe) [28]. Although it is known that the size, shape and charge of the TMC cations play a very important role in the construction of the inorganic main-group metal chalcogenide anions, a clear relationship between them still not observed and more compounds need to be synthesized for further understanding.…”

Surfactant-Thermal Syntheses, Structures, and Magnetic Properties of Mn–Ge–Sulfides/Selenides

“…[Mn(en) 2 29 The length of Mn−Se4 bond (2.858 Å) in compound 3 is much longer than its normal length of 2.5−2.6 Å. 27b (1,3-dapH)(puH)MnGeSe 4 (4).…”