Structure and Magnetic Studies on a Series of Two-Dimensional Iron(ii) Framework Materials with Varying Ligand Characteristics
Matthew A. D. Roxburgh A , Samantha Zaiter A , Xina I. B. Hudson A , Benjamin R. Mullaney A , John E. Clements A , Boujemaa Moubaraki B , Keith S. Murray B , Suzanne M. Neville A C and Cameron J. Kepert A C
+ Author Affiliations
- Author Affiliations
A School of Chemistry, The University of Sydney, Sydney, NSW 2006, Australia.
B School of Chemistry, Monash University, Melbourne, Vic. 3800, Australia.
C Corresponding authors. Email: suzanne.neville@sydney.edu.au; cameron.kepert@sydney.edu.au
Australian Journal of Chemistry 70(5) 623-631 https://doi.org/10.1071/CH16586
Submitted: 13 October 2016 Accepted: 25 February 2017 Published: 23 March 2017
Abstract
Targeting the general (4,4)-grid structural motif, we have prepared seven new coordination polymers in the general family [Fe(NCX)2(L)2]·(guest) (L = bis-pyridyl-type bridging ligands; X = S, Se) as an extension of the well-established spin crossover framework (SCOF) family. In all cases, the (4,4)-grid topology is formed by the bridging of octahedral iron(ii) sites in the equatorial plane by bis-pyridyl ligands of varying length, flexibility, and intermolecular interaction capacity. In particular, the six ligands n-(4-pyridyl)-isonicotinamide (pin), trans-1,2-bis(4′-pyridyl)ethane (tvp), 1,2-dibromo-1,2-bis(4′-pyridyl)ethane (dbbpe), bis(4-pyridyl)-1,2,4,5-tetrazine (bptz), 4,4′-bis(pyridyl)acetylene (bpac), and 1,4-bis(4-pyridylethynyl)benzene (bpeben) have been utilised. The seven new materials [Fe(NCS)2(pin)2]·2(MeCN) (pin-S), [Fe(tvp)2(NCS)2]·1/2(tvp)·(CH3CH2OH) (tvp-S), [Fe(dbbpe)2(NCS)2]·6(CH3CN) (dbbpe-S), [Fe(NCS)2(bptz)2]·2(CHCl3)·6(EtOH) (bptz-S), [Fe(NCSe)2(bptz)2]·4(CHCl3)·(EtOH)·(H2O) (bptz-Se), [Fe(NCS)2(bpac)2]·2(PrOH) (bpac-S), and [Fe(NCS)2(bpeben)2]·2(CHCl3) (bpeben-S) all form (4,4)-grids of varying size that are arranged in a parallel stacked topology. Despite being in the [FeN6] coordination environment known to be conducive to spin crossover, these materials all remain high-spin with thermal variation. These results are discussed in context with the large family of SCOFs that show varied spin crossover behaviours.
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