Iron(II) Mononuclear Materials Containing Functionalised Dipyridylamino-Substituted Triazine Ligands: Structure, Magnetism and Spin Crossover*
Hayley S. Scott A , Tamsyn M. Ross A , Stuart R. Batten A , Ian A. Gass A , Boujemaa Moubaraki A , Suzanne M. Neville A and Keith S. Murray A B
+ Author Affiliations
- Author Affiliations
A School of Chemistry, Monash University, Clayton, Vic. 3800, Australia.
B Corresponding author. Email: keith.murray@monash.edu
Australian Journal of Chemistry 65(7) 874-882 https://doi.org/10.1071/CH12052
Submitted: 30 January 2012 Accepted: 13 March 2012 Published: 16 May 2012
Abstract
The spin crossover effect in iron(II) materials containing the di-2-pyridylamine functional group has been investigated for the new nitrile-functionalised ligand DTAC (2,2′,2″,2″′-((6-(di(pyridin-2-yl)amino)-1,3,5-triazine-2,4 diyl)bis(azanetriyl))tetra acetonitrile). This ligand has successfully been incorporated into a family of materials of the general formula trans-[Fe(DTAC)2(anion)2], wherein we have systematically varied the trans-nitrogen donor anion from NCS, NCSe, N(CN)2 (dca; dicyanamide) to NCBH3 – thus forming the four mononuclear materials trans-[Fe(DTAC)2(NCS)2]·6MeCN (1), trans-[Fe(DTAC)2(NCSe)2]·6MeCN (2), trans-[Fe(DTAC)2(N(CN)2)2] (3) and trans-[Fe(DTAC)2 (NCBH3)2]·3MeCN (4)). We find that the materials with a weaker crystal field strength anion remain high spin over all temperatures (1 and 2) whereas the materials containing stronger crystal field strength anions undergo a thermally induced spin crossover (3 and 4). Structural analysis revealed that the packing interactions in the solid state and the degree of solvation also play a large role in the observed magnetic behaviour. Indeed, aged or rapidly precipitated samples of 2 show a spin transition above room temperature.
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