Preparation and structure of three solvatomorphs of the polymer [Co(dbM)2(4PtZ)]n:: spin canting depending on the supramolecular organization

被引:49
作者
Barrios, Leoni A.
Ribas, Joan
Aromi, Guillem
Ribas-Arino, Jordi
Gamez, Patrick
Roubeau, Olivier
Teat, Simon J.
机构
[1] Univ Barcelona, Dept Quim Inorgan, E-08028 Barcelona, Spain
[2] Univ Barcelona, Dept Quim Fis, CERQT, E-08028 Barcelona, Spain
[3] Leiden Univ, Inst Chem, Gorlaeus Labs, NL-2300 RA Leiden, Netherlands
[4] Univ Bordeaux 1, Ctr Rech Paul Pascal, F-33600 Pessac, France
[5] CCLRC Daresbury Lab, Warrington WA4 4AD, Cheshire, England
[6] Lawrence Berkeley Lab, Berkeley, CA 94720 USA
关键词
D O I
10.1021/ic7004979
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The syntheses and X-ray structures of three isomeric ID coordination polymers are reported. The complex [Co(dbM)(2)(MeOH)(2)] (1) was used as a precursor in these reactions. The preparation and structure of 1 is also presented; this mononuclear complex is in the cis configuration because this allows the formation of a network of intermolecular hydrogen bonds in the solid state. Reaction of 1 with 2,4,6-tris-(4-pyridyl)-1,3,5-triazine (4ptz) yields the polymers [Co(dbm)(2)(4ptz)](n).nTHF (2a), [Co(dbM)(2)(4ptZ)]n.0.75nTHF.0.5nEt(2)O (2b), and [Co(dbM)(2)(4ptZ)(n).3nDMF (2c) in the form of zigzag chains, instead of the expected honeycomb architectures. This is because of the establishment of extended pi-pi T stacking throughout these solids, which could not have occurred otherwise. Compounds 2a, 2b, and 2c are solvatomorphs, and formation of either one of them depends on the exact conditions of crystallization, which lead to significant differences in the supramolecular organization of the chains. Bulk magnetic measurements on 2a reveal weak antiferromagnetic exchange within the chains and small ordering throughout the solid that results in the manifestation of the phenomenon of spin canting, whereas for 2c the different supramolecular organization causes the antiferromagnetic exchange not to result in spin canting.
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页码:7154 / 7162
页数:9
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