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| Title: | Spin-frustrated complex, [FeIIFeIII(trans-1,4-cyclohexanedicarboxylate)₁.₅]∞: Interplay between single-chain magnetic behavior and magnetic ordering |
| Alternate Title: | Spin-frustrated complex, [FeIIFeIII(trans-1,4-cyclohexanedicarboxylate)1.5](Infinity): Interplay between single-chain magnetic behavior and magnetic ordering |
| Author (s): | Zheng, Yan-Zhen Xue, Wei Zhang, Wei-Xiong Tong, Ming-Liang Chen, Xiao-Ming Grandjean, Fernande Long, Gary John Ng, Seik-Weng Panissod, Pierre Drillon, Marc |
| Department/Lab Affiliations: | Chemistry |
| Keywords: | Electron spin magnetic spin frustration |
| Issue Date: | 2009-02 |
| Publisher: | American Chemical Society ACS |
| Citation: | Zheng, Yan-Zhen, Wei Xue, Wei-Xiong Zhang, Ming-Liang Tong, Xiao-Ming Chen, Fernande Grandjean, Gary J. Long, Seik-Weng Ng, Pierre Panissod, and Marc Drillon. Spin-Frustrated Complex, [FeIIFeIII(trans-1,4-cyclohexanedicarboxylate)1.5]∞: Interplay between Single-Chain Magnetic Behavior and Magnetic Ordering. Inorg. Chem., February 2009. |
| Abstract: | A three-dimensional mixed-valent iron(II,III) trans-1,4-cyclohexanedicarboxylate, 1,4-chdc, coordination polymer, [FeIIFeIII(μ4-O)(1,4-chdc)1.5]∞, 1, has been synthesized hydrothermally by mixing iron powder and 1,4-chdcH2 and investigated by X-ray diffraction, dc and ac magnetic susceptibility, and iron-57 Mssbauer spectroscopy over a wide range of temperatures. Single-crystal X-ray diffraction studies of 1 at 90(2), 293(2), and 473(2) K reveal a tetrahedral [FeII2(μ4-O)FeIII2(μ4-O)]6+ mixed-spin-chain structure with no change in the P space group but with subtle changes in the Fe−O and Fe···Fe distances with increasing temperature. These changes are associated with the electron delocalization observed by Mssbauer spectroscopy above 225 K. Magnetic studies reveal three different magnetic regimes in 1 between 2 and 320 K. Above 36 K 1 is a one-dimensional ferrimagnetic-like complex with frustration arising from competing exchange interactions between the iron(II) and iron(III) ions in the chains. Between 36 and 25 K the interchain interactions are non-negligible and 1 undergoes three-dimensional ordering at 32.16 K but with some residual fluctuations. Below 25 K the residual fluctuations slow and eventually freeze below 15 K; the small net moment of 0.22 μB per mole of 1 observed below 15 K may be attributed to a non-collinear or canted spin structure of the spins of the four iron ions in the [FeII2(μ4-O)FeIII2(μ4-O)]6+ chains. Below 32 K the Mssbauer spectra of 1 exhibit sharp sextets for both the iron(III) and iron(II) ions and are consistent with either a static long-range or a short-range magnetic ground state or a slow relaxation between two canted magnetic states that are indistinguishable at the observed spectral resolution. The 85 and 155 K spectra reveal no electron delocalization and correspond solely to fixed valence iron(II) and iron(III). Between 225 and 310 K the spectra reveal the onset of electron delocalization such that, at 295 to 310 K, 25, 25, and 50% of the iron in 1 is present as iron(II), iron(III), and iron(II/III) ions, respectively. The absence of any spectral line broadening associated with this electron delocalization and the coexistence of four doublets between 225 and 310 K indicate that the delocalization occurs through electron tunneling via vibronic coupling. The sudden increase in the tunneling rate beginning above about 260 K and the presence of a cusp in the magnetic susceptibility centered at about 275 K strongly suggest the existence of a charge order/disorder transition whose nature and order are discussed. |
| Type: | Article - Journal text |
| In Title: | Inorganic Chemistry |
| Copyright Notice: | This material is presented to ensure timely dissemination of scholarly and technical work. Copyright and all rights therein are retained by authors or by other copyright holders. All persons copying this information are expected to adhere to the terms and constraints invoked by each author's copyright. In most cases, these works may not be reposted without the explicit permission of the copyright holder. Pre-print: author cannot archive; Post-print: author cannot archive; FULL COPYRIGHT INFORMATION: |
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| title | Spin-frustrated complex, [FeIIFeIII(trans-1,4-cyclohexanedicarboxylate)₁.₅]∞: Interplay between single-chain magnetic behavior and magnetic ordering |
| title.alternative | Spin-frustrated complex, [FeIIFeIII(trans-1,4-cyclohexanedicarboxylate)1.5](Infinity): Interplay between single-chain magnetic behavior and magnetic ordering |
| contributor.author | Zheng, Yan-Zhen |
| contributor.author | Xue, Wei |
| contributor.author | Zhang, Wei-Xiong |
| contributor.author | Tong, Ming-Liang |
| contributor.author | Chen, Xiao-Ming |
| contributor.author | Grandjean, Fernande |
| contributor.author | Long, Gary John |
| contributor.author | Ng, Seik-Weng |
| contributor.author | Panissod, Pierre |
| contributor.author | Drillon, Marc |
| contributor.deptlab | Chemistry |
| contributor.sponsor | National Fund for Scientific Research, Belgium |
| contributor.sponsor | National Natural Science Foundation of China |
| contributor.sponsor | Science and Technology Department of Guangdong Province |
| subject | Electron spin |
| subject | magnetic spin frustration |
| date.issued | 2009-02 |
| publisher | American Chemical Society ACS |
| identifier.citation | Zheng, Yan-Zhen, Wei Xue, Wei-Xiong Zhang, Ming-Liang Tong, Xiao-Ming Chen, Fernande Grandjean, Gary J. Long, Seik-Weng Ng, Pierre Panissod, and Marc Drillon. Spin-Frustrated Complex, [FeIIFeIII(trans-1,4-cyclohexanedicarboxylate)1.5]∞: Interplay between Single-Chain Magnetic Behavior and Magnetic Ordering. Inorg. Chem., February 2009. |
| identifier.pub.URI | |
| description.abstract | A three-dimensional mixed-valent iron(II,III) trans-1,4-cyclohexanedicarboxylate, 1,4-chdc, coordination polymer, [FeIIFeIII(μ4-O)(1,4-chdc)1.5]∞, 1, has been synthesized hydrothermally by mixing iron powder and 1,4-chdcH2 and investigated by X-ray diffraction, dc and ac magnetic susceptibility, and iron-57 Mssbauer spectroscopy over a wide range of temperatures. Single-crystal X-ray diffraction studies of 1 at 90(2), 293(2), and 473(2) K reveal a tetrahedral [FeII2(μ4-O)FeIII2(μ4-O)]6+ mixed-spin-chain structure with no change in the P space group but with subtle changes in the Fe−O and Fe···Fe distances with increasing temperature. These changes are associated with the electron delocalization observed by Mssbauer spectroscopy above 225 K. Magnetic studies reveal three different magnetic regimes in 1 between 2 and 320 K. Above 36 K 1 is a one-dimensional ferrimagnetic-like complex with frustration arising from competing exchange interactions between the iron(II) and iron(III) ions in the chains. Between 36 and 25 K the interchain interactions are non-negligible and 1 undergoes three-dimensional ordering at 32.16 K but with some residual fluctuations. Below 25 K the residual fluctuations slow and eventually freeze below 15 K; the small net moment of 0.22 μB per mole of 1 observed below 15 K may be attributed to a non-collinear or canted spin structure of the spins of the four iron ions in the [FeII2(μ4-O)FeIII2(μ4-O)]6+ chains. Below 32 K the Mssbauer spectra of 1 exhibit sharp sextets for both the iron(III) and iron(II) ions and are consistent with either a static long-range or a short-range magnetic ground state or a slow relaxation between two canted magnetic states that are indistinguishable at the observed spectral resolution. The 85 and 155 K spectra reveal no electron delocalization and correspond solely to fixed valence iron(II) and iron(III). Between 225 and 310 K the spectra reveal the onset of electron delocalization such that, at 295 to 310 K, 25, 25, and 50% of the iron in 1 is present as iron(II), iron(III), and iron(II/III) ions, respectively. The absence of any spectral line broadening associated with this electron delocalization and the coexistence of four doublets between 225 and 310 K indicate that the delocalization occurs through electron tunneling via vibronic coupling. The sudden increase in the tunneling rate beginning above about 260 K and the presence of a cusp in the magnetic susceptibility centered at about 275 K strongly suggest the existence of a charge order/disorder transition whose nature and order are discussed. |
| type | Article - Journal |
| type.DCMIType | text |
| relation.isPartOf | Inorganic Chemistry |
| rights | This material is presented to ensure timely dissemination of scholarly and technical work. Copyright and all rights therein are retained by authors or by other copyright holders. All persons copying this information are expected to adhere to the terms and constraints invoked by each author's copyright. In most cases, these works may not be reposted without the explicit permission of the copyright holder. |
| rights | Pre-print: author cannot archive; Post-print: author cannot archive; |
| rights.URI | |
| rights.URI | |
| identifier.persist.URI | |
| date.available | 2009-03-13T16:00:41Z |