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Contents Vol 67(11)

Thermal Spin Crossover Behaviour of Two-Dimensional Hofmann-Type Coordination Polymers Incorporating Photoactive Ligands

Florence Ragon A , Korcan Yaksi A , Natasha F. Sciortino A , Guillaume Chastanet B , Jean-François Létard B , Deanna M. D’Alessandro A , Cameron J. Kepert A and Suzanne M. Neville A C
+ Author Affiliations
- Author Affiliations

A School of Chemistry, The University of Sydney, Sydney, NSW 2006, Australia.

B CNRS, Université de Bordeaux, ICMCB, UPR 9048, F-33600 Pessac, France.

C Corresponding author. Email: suzanne.neville@sydney.edu.au

Australian Journal of Chemistry 67(11) 1563-1573 https://doi.org/10.1071/CH14188
Submitted: 29 March 2014  Accepted: 18 April 2014   Published: 26 June 2014

Abstract

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.


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