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Spin Crossover and Solvate Effects in 1D Fe II Chain Compounds Containing Bis(dipyridylamine)‐Linked Triazine Ligands
Author(s) -
Ross Tamsyn M.,
Moubaraki Boujemaa,
Turner David. R.,
Halder Gregory J.,
Chastanet Guillaume,
Neville Suzanne M.,
Cashion John D.,
Létard JeanFrançois,
Batten Stuart R.,
Murray Keith S.
Publication year - 2011
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/ejic.201000876
Subject(s) - chemistry , spin crossover , solvent , ligand (biochemistry) , substituent , denticity , stereochemistry , supramolecular chemistry , triazine , medicinal chemistry , solvent effects , intermolecular force , crystallography , crystal structure , molecule , polymer chemistry , organic chemistry , biochemistry , receptor
A series of 1D polymeric Fe II spin crossover (SCO) compounds of type trans ‐[Fe II (NCX) 2 (L)] · Solvent has been synthesised {L = DPPyT = 1‐[4,6‐bis(dipyridin‐2‐ylamino)‐1,3,5‐triazin‐2‐yl]pyridin‐4(1 H )‐one for 1 – 4 ; NCX = NCS – for 1 and 2 , NCSe – for 3 and 4 ; Solvent = 2.5CH 2 Cl 2 for 1 , 2CHCl 3 · 0.5CH 3 OH for 2 and 4 , CH 2 Cl 2 for 3 ; L = DPT (6‐phenoxy‐ N 2 , N 2 , N 4 , N 4 ‐tetra‐2‐pyridinyl‐1,3,5‐triazine‐2,4‐diamine) for 5 ; NCX = NCS – for 5 ; Solvent = 2CH 3 OH · H 2 O for 5 ; L = DQT {4‐[4,6‐bis(dipyridin‐2‐ylamino)‐1,3,5‐triazin‐2‐yloxy]phenol} for 6 – 8 ; NCX – = NCS – for 6 ; Solvent = 2CH 2 Cl 2 for 6 ; NCX – = NCSe – for 7 ; Solvent = CH 2 Cl 2 · CH 2 ClCH 2 Cl for 7 ; NCX – = NCSe – for 8 ; Solvent = 1.5CH 2 Cl 2 · 0.5CH 3 OH for 8 }. Two mononuclear complexes, trans ‐[Fe II (NCS) 2 (DPT) 2 ] · 2CH 3 OH ( 9 ) and trans ‐[Fe II (NCSe) 2 (DPT) 2 ] · 2CH 3 OH ( 10 ), contained the L ligand in a terminal bidentate coordination mode. As well as variations made in the NCX – ligands, variations were also made in substituent groups on the s ‐triazine “core” of L to investigate their intermolecular/supramolecular role in crystal packing and, thus, their influence on SCO properties. All the complexes crystallised as solvates, and the influence of the latter on the magnetism and spin transitions was explored. A wide range of physical methods was employed, as a function of temperature, viz. crystallography, PXRD (synchrotron), susceptibilities, LIESST and Mössbauer effect, in order to probe magnetostructural correlations in these 1D families. New examples of half‐crossovers, with ordered –LS–HS–LS–HS– intrachain states existing below T 1/2 , have been observed and comparisons made to related one‐ or two‐step systems. All the observed transitions are gradual and non‐hysteretic, and brief comments are made in relation to recent theoretical models for cooperativity, developed elsewhere.