RAGON, Florence; YAKSI, Korcan; SCIORTINO, Natasha F.; CHASTANET, Guillaume; LÉTARD, Jean-Francois; D’ALESSANDRO, Deanna M.; KEPERT, Cameron J.; NEVILLE, Suzanne M.

doi:10.1071/CH14188

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RAGON, Florence
School of Chemistry

YAKSI, Korcan
School of Chemistry

SCIORTINO, Natasha F.
School of Chemistry

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Australian Journal of Chemistry. 2014, vol. 67, n° 11, p. 1563-1573

CSIRO Publishing

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Two spin crossover (SCO)-active 2D Hofmann-type framework materials, [Fe(3-PAP)2Pd(CN)4] (A) and [Fe(4-PAP)2Pd(CN)4] (B) containing the photoactive azo-benzene-type ligands 3-phenylazo-pyridine (3-PAP) and 4-phenylazo-pyridine (4-PAP) were prepared. These materials form non-porous Hofmann-type structures whereby 2D [FeIIPd(CN)4] grids are separated by 3- or 4-PAP ligands. The iron(ii) sites of both materials (A and B) undergo abrupt and hysteretic spin transitions with characteristic transition temperatures T1/2↓,↑: 178, 190 K (ΔT: 12 K) and T1/2↓,↑: 233, 250 K (ΔT: 17 K), respectively. Photo-magnetic characterisations reveal light-induced excited spin state trapping (LIESST) activity in both A and B with characteristic T(LIESST) values of 45 and 40 K. Although both free ligands show trans- to-cis isomerisation in solution under UV-irradiation, as evidenced via absorption spectroscopy, such photo-activity was not observed in the ligands or complexes A and B in the solid state. Structural analysis of a further non-SCO active isomer to B, [Fe(4-PAP)2Pd(CN)4]·1/2(4-PAP) (B·(4-PAP)), which contains free ligand in the pore space is reported.< Réduire

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Thermal spin crossover behaviour of two-dimensional Hofmann-type coordination polymers incorporating photoactive ligands

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