Radical Salts of Bis(ethylenediseleno)tetrathiafulvalene with Paramagnetic Tris(oxalato)metalate Anions
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- 作者：Eugenio Coronado ; Simona Curreli ; Carlos Gimé ; nez-Saiz ; Carlos J. Gó ; mez-Garcí ; a ; Antonio Alberola
- 刊名：Inorganic Chemistry
- 出版年：2006
- 出版时间：December 25, 2006
- 年：2006
- 卷：45
- 期：26
- 页码：10815 - 10824
- 全文大小：487K
- 年卷期：v.45,no.26(December 25, 2006)
- ISSN：1520-510X
文摘
The synthesis, crystal structure, and physical characterization of five new radical salts formed by the organic donorbis(ethylenediseleno)tetrathiafulvalene (BEST) and the paramagnetic tris(oxalato)metalate anions [M(C2O4)3]3- (M= FeIII and CrIII) are reported. The salts isolated are (BEST)4[M(C2O4)3]·PhCOOH·H2O with MIII = Cr (1) or Fe (2)(crystal data: 1, triclinic, space group P
with a = 14.0999(4) Å, b = 15.3464(4) Å, c = 19.5000(4) Å, 
=76.711(5)
, 
= 71.688(5), 
= 88.545(5), V = 3893.5(2) Å3, and Z = 2; 2, triclinic, space group P with a =14.0326(3) Å, b = 15.1981(4) Å, c = 19.4106(4) Å, = 76.739(5), = 71.938(5), = 88.845(5), V =3824.9(2) Å3, and Z = 2), (BEST)4[M(C2O4)3]·1.5H2O with MIII = Cr (3) or Fe (4) (crystal data: 3, monoclinic,space group C2/m with a = 33.7480(10) Å, b = 12.3151(7) Å, c = 8.8218(5) Å, = 99.674(5), V = 3614.3(3)Å3, and Z = 2; 4, monoclinic, space group C2/m with a = 33.659(6) Å, b = 12.248(2) Å, c = 8.759(2) Å, =99.74(3), V = 3558.9(12) Å3, and Z = 2), and (BEST)9[Fe(C2O4)3]2·7H2O (5) (crystal data: triclinic, space groupP with a = 12.6993(3) Å, b = 18.7564(4) Å, c = 18.7675(4) Å, = 75.649(5), = 107.178(5), =79.527(5), V = 3977.5(3) Å3, and Z = 1). The structures of all these salts consist of alternating layers of theorganic donors and tris(oxalato)metalate anions. In 1 and 2 the anionic layers contain also benzoic acid moleculesH-bonded to the terminal oxygen atoms of the anions. In all salts the organic layers adopt -type packings. Alongthe parallel stacks the donors form dimers in 3 and 4, trimers in 5, and tetramers in 1 and 2. All the compoundsare paramagnetic semiconductors with high room-temperature conductivities and magnetic susceptibilities dominatedby the Fe- or Cr-containing anions.
with a = 14.0999(4) Å, b = 15.3464(4) Å, c = 19.5000(4) Å, =76.711(5), = 71.688(5), = 88.545(5), V = 3893.5(2) Å3, and Z = 2; 2, triclinic, space group P with a =14.0326(3) Å, b = 15.1981(4) Å, c = 19.4106(4) Å, = 76.739(5), = 71.938(5), = 88.845(5), V =3824.9(2) Å3, and Z = 2), (BEST)4[M(C2O4)3]·1.5H2O with MIII = Cr (3) or Fe (4) (crystal data: 3, monoclinic,space group C2/m with a = 33.7480(10) Å, b = 12.3151(7) Å, c = 8.8218(5) Å, = 99.674(5), V = 3614.3(3)Å3, and Z = 2; 4, monoclinic, space group C2/m with a = 33.659(6) Å, b = 12.248(2) Å, c = 8.759(2) Å, =99.74(3), V = 3558.9(12) Å3, and Z = 2), and (BEST)9[Fe(C2O4)3]2·7H2O (5) (crystal data: triclinic, space groupP with a = 12.6993(3) Å, b = 18.7564(4) Å, c = 18.7675(4) Å, = 75.649(5), = 107.178(5), =79.527(5), V = 3977.5(3) Å3, and Z = 1). The structures of all these salts consist of alternating layers of theorganic donors and tris(oxalato)metalate anions. In 1 and 2 the anionic layers contain also benzoic acid moleculesH-bonded to the terminal oxygen atoms of the anions. In all salts the organic layers adopt -type packings. Alongthe parallel stacks the donors form dimers in 3 and 4, trimers in 5, and tetramers in 1 and 2. All the compoundsare paramagnetic semiconductors with high room-temperature conductivities and magnetic susceptibilities dominatedby the Fe- or Cr-containing anions.