Low temperature route towards new materials: solvothermal synthesis of metal chalcogenides in ethylenediamine

Review. Solvothermal Synthesis and Structure of Chalcogenidoarsenate Anions

“…The solubility of inorganic starting materials such as metals, chalcogens and metal chalcogenides is greatly enhanced at elevated temperatures in such strongly polarizing media, and the prevailing reaction conditions in both techniques are suitable to support ion diffusion, but still mild enough to leave solution species such as chains and rings intact to participate in the construction of solid-state phases. A range of polar fluids such as H 2 O [2], CH 3 OH [3], NH 3 [2], en (= ethylenediamine) [4], dien (= diethylenetriamine) [5], tren (= tris(2-aminoethyl)amine) [6], and CH 3 CN [7] have been employed as reaction media for the solvothermal synthesis of chalcogenidoarsenates. However, the solubility of the inorganic components must often be enhanced by the addition of a mineralizer [8], which can be de-0932-0776 / 10 / 0800-0918 $ 06.00 c 2010 Verlag der Zeitschrift für Naturforschung, Tübingen · http://znaturforsch.com fined as a complexing agent capable of transporting ions from a starting material of low solubility to the site of product nucleation.…”

“…In this and other relevant coordination polyhedra (i. e. ψ-ME 3 tetrahedra and ψ-ME 5 octahedra) of trivalent Group 15 elements M, use of the Greek letter ψ implies that one site is formally occupied by a non-bonded electron pair. The effective [26] [Sr(en) 4 ] 2 (As 3 Se 6 )Cl [29] [Fe(phen) 3 ]As 3 S 6 · dien · 7H 2 O [27], [Mn(dien) 2 ] 3 (As 3 Se 6 ) 2 [30] refs. [13,28] restriction to ψ-AsE 3 (E = S, Se) tetrahedra as the basic building units for the construction of oligomeric and polymeric anions leads to a striking paucity in the number of structural types adopted by the thio-and selenidoarsenates(III) in comparison to the analogous chalcogenidoantimonates(III) [9].…”

“…Although all types of chalcogenidoarsenate anions will be considered in the present review, its emphasis will, therefore, be placed on recent developments in the period 1998 -2009. One currently expanding area of interest involves the employment of transition metal-polyamine or -polyimine fragments such as {Mn(dien)} 2+ , {Mn(tren)} 2+ or {Mn(terpy)} 2+ (terpy = 2,2 : 6 ,2 -terpyridine) as structure-directing agents for the construction of novel ternary anions [4,11]. The metal atoms of such cations can be connected with the terminal chalcogens of oligomeric or polymeric anions to prevent their further propagation or can be directly incorporated into anionic or neutral networks when two or more free coordination sites are available in the fragment.…”

Crystal structure of 2-aminoethylammonium tris-(1,2-ethanediamine) zinc(II)tetraselenoantimonate(V), (C2H9N2)[Zn(C2H8N2)3][SbSe4], C8H33N8SbSe4Zn

“…The solvothermal reaction in amine has proven to be aversatile route for the syntheses of chalcogenometalates [1][2][3][4]. In recent years, an increasingi nteresti nc halcogenidef ramework structuresh as been observed duet ot heir promisingc ombination of zeotypes tructures with novel properties [5].…”

“…Although, al arge number of thioantiomonates (Sb x S y )exhibiting avariety of polymeric complex anions have been well explored, the chemistry of higher chalcogenoantimonates (Sb x Se y or Sb x Te y )isless developed [4]. Our recent investigation on the selenoantimonate system using transition metals in ethylenediamine led to an ew (C 2 …”