Iron Lanthanide Phosphonate Clusters: {Fe(6)Ln(6)P(6)} Wells-Dawson-like Structures with D-3d Symmetry

Pineda EM, Tuna F, Zheng Y-Z, Teat SJ, Winpenny REP, Schnack J, McInnes EJL (2014)
Inorganic Chemistry 53(6): 3032-3038.

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Abstract
Reaction of [Fe-3(mu(3)-O)(O2C'Bu)(6)(HO2C'Bu)(3))](O2C'Bu) and [Ln(2)(O2C'Bu)(6)(HO2C'Bu)(6)] (Ln = lanthanide) with three different phosphonic acids produce a family of highly symmetrical {Fe(6)Ln(6)P(6)} clusters with general formula [Fe(6)Ln(6)(mu(3)-O)(2)(CO3)(O3PR)(6)(O2C'Bu)(18)], where R = methyl 1, phenyl 2, or n-hexyl 3. All the clusters present an analogous metal frame to the previously reported {Ni(6)Ln(6)P(6)} both being related to the well-known Wells-Dawson ion from polyoxometallate chemistry. These highly symmetrical clusters have, or approximate very closely to, D-3d point symmetry. Both Fe-III and Gd-III ions are magnetically isotropic and could thus exhibit promising magnetocaloric properties; hence we investigated the {Fe6Gd6P6} compounds accordingly. Modeling the magnetic data of [Fe6Gd6(mu(3)-O)(2)(CO3)(O3PPh)(6)(O2C'Bu)(18)] by the finite-temperature Lanczos method gave a strong antiferromagnetic Fe center dot center dot center dot Fe interaction (J(Fe-Fe) = -30 cm(-1)) and very weak Gd center dot center dot center dot Gd and Gd center dot center dot center dot Fe exchange interactions (vertical bar J vertical bar < 0.1 cm(-1)). The strong antiferromagnetic Fe center dot center dot center dot Fe interaction could account for the relatively smaller -Delta S-m value observed, compared against the {Ni6Gd6P6} analogues.
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Pineda EM, Tuna F, Zheng Y-Z, et al. Iron Lanthanide Phosphonate Clusters: {Fe(6)Ln(6)P(6)} Wells-Dawson-like Structures with D-3d Symmetry. Inorganic Chemistry. 2014;53(6):3032-3038.
Pineda, E. M., Tuna, F., Zheng, Y. - Z., Teat, S. J., Winpenny, R. E. P., Schnack, J., & McInnes, E. J. L. (2014). Iron Lanthanide Phosphonate Clusters: {Fe(6)Ln(6)P(6)} Wells-Dawson-like Structures with D-3d Symmetry. Inorganic Chemistry, 53(6), 3032-3038.
Pineda, E. M., Tuna, F., Zheng, Y. - Z., Teat, S. J., Winpenny, R. E. P., Schnack, J., and McInnes, E. J. L. (2014). Iron Lanthanide Phosphonate Clusters: {Fe(6)Ln(6)P(6)} Wells-Dawson-like Structures with D-3d Symmetry. Inorganic Chemistry 53, 3032-3038.
Pineda, E.M., et al., 2014. Iron Lanthanide Phosphonate Clusters: {Fe(6)Ln(6)P(6)} Wells-Dawson-like Structures with D-3d Symmetry. Inorganic Chemistry, 53(6), p 3032-3038.
E.M. Pineda, et al., “Iron Lanthanide Phosphonate Clusters: {Fe(6)Ln(6)P(6)} Wells-Dawson-like Structures with D-3d Symmetry”, Inorganic Chemistry, vol. 53, 2014, pp. 3032-3038.
Pineda, E.M., Tuna, F., Zheng, Y.-Z., Teat, S.J., Winpenny, R.E.P., Schnack, J., McInnes, E.J.L.: Iron Lanthanide Phosphonate Clusters: {Fe(6)Ln(6)P(6)} Wells-Dawson-like Structures with D-3d Symmetry. Inorganic Chemistry. 53, 3032-3038 (2014).
Pineda, Eufemio Moreno, Tuna, Floriana, Zheng, Yan-Zhen, Teat, Simon J., Winpenny, Richard E. P., Schnack, Jürgen, and McInnes, Eric J. L. “Iron Lanthanide Phosphonate Clusters: {Fe(6)Ln(6)P(6)} Wells-Dawson-like Structures with D-3d Symmetry”. Inorganic Chemistry 53.6 (2014): 3032-3038.
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