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Structural and physical properties of the ferromagnetic tris-dithiooxalato compounds, A[(MCrIII)-Cr-II(C2S2O2)(3)], with A(+) = N(n-CnH2n+1)(4)(+) (n=3-5) and P(C6H5)(4)(+) and M-II = Mn, Fe, Co, and Ni
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UNSPECIFIED. (2003) Structural and physical properties of the ferromagnetic tris-dithiooxalato compounds, A[(MCrIII)-Cr-II(C2S2O2)(3)], with A(+) = N(n-CnH2n+1)(4)(+) (n=3-5) and P(C6H5)(4)(+) and M-II = Mn, Fe, Co, and Ni. INORGANIC CHEMISTRY, 42 (4). pp. 986-996. ISSN 0020-1669
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Official URL: http://dx.doi.org/10.1021/ic020302x
Abstract
The structural and magnetic properties of the tris-dithiooxalato salts, A[(MCr)-Cr-II(C2S2O2)(3)], have been investigated with A(+) = PPh4+, N(n-CnH2+1)(4)(+), with n = 3-5, where M-II is Mn, Fe, Co, and Ni. With the exception of A[MnCr-(C2S2O2)(3)], all the salts are ferromagnets with Curie temperatures, T-c between 5 and 16 K. In contrast to the corresponding oxalates which are ferromagnetic, the A[MnCr(C2S2O2)(3)] compounds are paramagnetic above 2 K. Powder neutron diffraction studies of d(20)-PPh4[FeCr(C2S2O2)(3)] indicate that no structural phase transitions occur between 2.4 and 285 K and that the coefficient of linear expansion is four times larger for the c-axis than for the a-axis. The crystal structure refined from powder neutron diffraction data confirms the honeycomb layer arrangement observed in the related bimetallic tris-oxalate salts. The Mbssbauer spectra reveal that the iron(II) in PPh4[FeCr(C2S2O2)(3)] is coordinated mainly to six oxygen atoms of the dithiooxalato ligand but with a minor component of sulfur coordination that increases with aging of the sample; the iron(II) is high-spin in both cases. Powder neutron diffraction profiles of d(20)-PPh4[FeCr(C2S2O2)(3)] below T-c show magnetic intensity with a q = 0 propagation vector, confirming the presence of ferromagnetic order.
| Item Type: | Journal Article |
|---|---|
| Subjects: | Q Science > QD Chemistry |
| Journal or Publication Title: | INORGANIC CHEMISTRY |
| Publisher: | AMER CHEMICAL SOC |
| ISSN: | 0020-1669 |
| Date: | 24 February 2003 |
| Volume: | 42 |
| Number: | 4 |
| Number of Pages: | 11 |
| Page Range: | pp. 986-996 |
| Identification Number: | 10.1021/ic020302x |
| Publication Status: | Published |
| URI: | http://wrap.warwick.ac.uk/id/eprint/10010 |
Data sourced from Thomson Reuters' Web of Knowledge
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