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Influence of Hydrogen Bonding on the Hysteresis Width in Iron(II) Spin‐Crossover Complexes
Author(s) -
Weber Birgit,
Bauer Wolfgang,
Pfaffeneder Toni,
Dîrtu Marinela M.,
Naik Anil D.,
Rotaru Aurelian,
Garcia Yann
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.201100394
Subject(s) - chemistry , spin crossover , spin transition , crystallography , hysteresis , thermal hysteresis , hydrogen bond , intermolecular force , imidazole , stereochemistry , molecule , thermodynamics , condensed matter physics , phase transition , organic chemistry , physics
A detailed investigation on the properties of the high‐temperature and low‐temperature modifications of the iron(II) spin‐crossover complex [FeL1(HIm) 2 ] ( 1) and its isotopic deuterium‐labelled analogue [FeL1(DIm) 2 ] ( 1 D), and the pair [FeL2(azpy)] · MeOH/[FeL2(azpy)] · CD 3 OD/[FeL2(azpy)] ( 2· MeOH/ 2· CD 3 OD/ 2 ), in which L1 and L2 are tetradentate N 2 O 2 2– ‐coordinating Schiff base like ligands, L1 = {diethyl( E , E )‐2,2′‐[1,2‐phenylbis(iminomethylidyne)]bis[3‐oxobutanoate](2–)‐ N , N ′, O 3 , O 3 ′}, L2 = {2,2′‐[1,2‐phenylbis(iminomethylidyne)]bis[1‐phenylbutane‐1,3‐dione](2–)‐ N , N ′, O 3 , O 3′ },HIm = imidazole, and azpy = 4,4′‐azopyridine, is presented. All complexes except 2 show a cooperative spin transition with hysteresis widths between approximately 5 K ( 1 LT and 1 LT D), 70 K ( 1 HT[9] and 1 HT D, around room temperature), and 80 K ( 2· MeOH and 2· CD 3 OD). In all cases, an influence of the H/D exchange on the transition temperature and the hysteresis width is observed. For 1 HT , first‐order reversal curves (FORCs) have been recorded, and a statistical analysis gives the interaction parameter J = 560 K, indicating strong intermolecular interactions. X‐ray structural analysis of the different samples ( 1 HT[9] and 1 HT D: HS; 1 LT and 1 LT D: LS; and 2· MeOH and 2· CD 3 OD: HS) gives a deeper insight into the molecular packing in the crystals and helps explain the increase of cooperative interactions during the spin transition. In all cases, one hydrogen bond involves an oxygen atom of the Schiff base like ligand that serves as a donor for the iron centre. The influence of this hydrogen bond on the ligand field strength of the iron centre is discussed and a new model is developed to explain the observed connection between hydrogen bonds and exceptionally wide hysteresis loops for the complexes presented in this work and other examples from the literature.