New extended magnetic systems based on oxalate and iron(III) ions

被引:37
作者
Armentano, Donatella [1 ]
Mastropietro, Teresa F. [1 ]
De Munno, Giovanni [1 ]
Rossi, Patrizia [2 ]
Lloret, Francesc [3 ]
Julve, Miguel [3 ]
机构
[1] Univ Calabria, Dipartmento Chim, I-87036 Arcavacata Di Rende, Italy
[2] Univ Florence, Dipartimento Energet, I-50134 Florence, Italy
[3] Univ Valencia, Dept Quim Inorgan, Inst Ciencia Mol, Valencia, Spain
关键词
D O I
10.1021/ic702403h
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
A series of oxalate-bridged iron(Ill) complexes have been synthesized by the reaction of FeCl3 with oxalic acid (H(2)ox) and XCl, where X is a substituted univalent ammonium or an alkaline cation. We have obtained basically two different types of compounds by varying the nature and the shape of the counterion, with the dimensionality of the resulting product being strongly influenced by the counterion. Three-dimensional (3D) networks of oxo- and oxalato-bridged iron(III) ions of the general formula {X-2[Fe2O(ox)(2)Cl-2] center dot pH(2)O}(n) have been obtained for X = Li+ (1), Na+ (2), and K+ (3) with p = 4 and X = MeNH3+ (4), Me2NH2+ (5), and EtNH3+ (6) with p = 2. Similar 3D hydroxo- and oxalato-bridged iron(III) networks of the formula {X[Fe-2(OH)(ox)(2)Cl-2] center dot 2H(2)O}(n) resulted for X = EtNH3+ (7a) and PrNH3+ (8). Compound 7a undergoes a solid-to-solid transformation, leading to a new species of the formula {(H3O)(EtNH3)[Fe2O(ox)(2)Cl-2] center dot H2O}(n) (7b). Chainlike compounds of the formula {X-2[Fe-2(ox)(2)Cl-4] center dot pH(2)O}(n) [X = Me2NH2+(9, P = 1), Me3NH+ (10, p = 2), and Me4N+ (11, p = 0)] have been obtained for the bulkier alkylammonium cations. Magnetic susceptibility measurements in the temperature range 1.9-295 K show the occurrence of weak ferromagnetic ordering due to spin canting in the 3D networks 1 -8, with the value of the critical temperature (T,) varying with the cation in the range 26 K (2) to 70 K (8) without significant structural modifications. The last three one-dimensional compounds exhibit the typical behavior of antiferromagnetically coupled chains of interacting spin sextets [J = -8.3 (9), -6.9 (10), and -8.4 (11) cm(-1) with H = -J Sigma iSiSi+1].
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收藏
页码:3772 / 3786
页数:15
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