Solvothermal and ionothermal syntheses and structures of amine- and/or (poly-)chalcogenide coordinated metal complexes

Abstract

A series of five compounds, namely [Ba(trien) 2 ] 3 [SbSe 4 ] 2 ·trien (1) (trien = diethylenetriamine), [(Se 3 )Cr(en) 2 (Se 2 )Cr(en) 2 (Se 3 )] 2 (2) (en = ethylenediamine), [(pren) 3 Eu(Te 3 ) 2 Eu(pren) 3 ] (3) (pren = 1,3-diaminopropane), [(en) 4 Ba(pren)Ba(en) 4 ](Te 3 ) 2 (4) and [enH] 4 [Sn 2 Se 6 ] (5), which illustrate the transition of classical polychalcogenides to metalates, are presented, where mixed amine/ (poly-)chalcogenide interaction with metal centers are in the focus of interest. A conventional aminothermal synthesis is discussed in comparison with ionothermal approaches. The compounds are considered useful precursors to study in situ interconversion of selenido-and telluridometalates under ionothermal conditions.

Synthese kristalliner Chalkogenide in ionischen Flüssigkeiten

“…Eine ionothermale Behandlung von Chalkogenidotetrelatsalzen oder entsprechenden Mischungen der Elemente führte zur Bildung neuer Salze von sehr einfachen oder sehr komplexen Chalkogenidotetrelatanionen – je nach Reaktionsbedingungen. Orangefarbene Plättchen von [enH] 4 [Sn 2 Se 6 ] ( 10 ) entstanden bei viertägigem Erhitzen von Li 4 [Sn 2 Se 6 ] mit en in [C 4 C 1 im][BF 4 ] auf 100 °C . Interessanterweise wurden die Alkalimetallkationen des Ausgangsstoffs hier nicht vom Kation der ionischen Flüssigkeit verdrängt, sondern von protonierten en‐Molekülen.…”

Discrete Supertetrahedral Tn Chalcogenido Clusters Synthesized in Ionic Liquids: Crystal Structures and Photocatalytic Activity

“…[45] Other types of discrete metal chalcogenide clusters have also been documented. [19,49,[64][65][66][67][68][69][70][71][72][73][74][75][76][77][78] All the discrete supertetrahedral Tn chalcogenido clusters synthesized in ILs thus far are summarized in Table 1, and the space group, band gap and synthetic conditions are listed as well. Noticeably, [Bmmim]Cl (Figure 2, left; Bmmim = 1-butyl-2,3-dimethylimidazolium) was widely adopted in the synthetic process.…”

“…The syntheses of discrete supertetrahedral T n chalcogenido clusters, however, were still elusive until we firstly reported on the syntheses of T5 clusters in ILs [45] . Other types of discrete metal chalcogenide clusters have also been documented [19,49,64–78] …”

Synthesis of Crystalline Chalcogenides in Ionic Liquids

“…Ionothermal treatment of either chalcogenidotetrelate salts or the according element mixtures led to the formation of novel salts of rather simple or rather complex chalcogenidotetrelate anions, depending on the reaction conditions. Orange plates of [enH] 4 [Sn 2 Se 6 ] ( 10 ) were obtained upon heating Li 4 [Sn 2 Se 6 ] with en in [C 4 C 1 im][BF 4 ] at 100 °C for four days . Interestingly, protonated en molecules and not an ionic liquid cation replaced the alkali metal cation of the starting material.…”