ABSTRACT
Homoleptic complexes [Fe(4bt)3](ClO4)2 (1), [Fe(2bt)3](ClO4)2 (2), and [Fe(3tpH)3](ClO4)2 (3) were obtained by a reaction between the Fe(II) precursor salt and the corresponding thiazole-based bidentate ligand (L = 4bt = 4,4'-bithiazole, 2bt = 2,2'-bithiazole, 3tpH = 3-(thiazol-2-yl)pyrazole). X-ray crystal structure determination revealed crystallization of solvent-free complex 1, a solvate 2·MeOH, and a co-crystal 3·2(3tpH). The crystal packing of all these complexes is dominated by one-dimensional interactions between the [Fe(L)3]2+ cations. These interactions are stronger in 2·MeOH and 3·2(3tpH), leading to cooperative and slightly hysteretic transitions between the high-spin and low-spin electronic configurations at â¼235 K and 159 K, respectively. In contrast, weaker intermolecular interactions in 1 result in a gradual spin crossover above 300 K, with the maximum fraction of the HS state â¼25% achieved at 400 K. Complexes 2 and 3·2(3tpH) exhibit light-induced excited spin state trapping (LIESST) under irradiation with white light or a 532 nm laser at 5 K. After the photoexcitation, the trapped metastable HS state relaxes to the ground LS state with the average relaxation temperature of 81 K and 68 K, respectively. Examination of the relaxation dynamics by optical absorption spectroscopy on a single crystal of 3·2(3tpH) revealed the sigmoidal shape of the relaxation curves at lower temperatures, attributed to cooperative effects, as well as a plateau at â¼10% of the HS fraction at intermediate temperatures, hinting at a more complex mechanism for the relaxation of the LIESST phase in this material.
ABSTRACT
A heteroleptic spin-crossover (SCO) complex, [Fe(tpma)(xnap-bim)](ClO4)2 (1; tpma = tris(2-pyridylmethyl)amine, xnap-bim = 8,15-dihydrodiimidazo[1,2-a:2',1'-c]naphtho[2,3-f][1,4]diazocine), has been obtained by reacting a Fe(II) precursor salt with tetradentate tpma and bidentate xnap-bim ligands. Depending on crystallization conditions, two different solvates have been obtained, 1·2.25py·0.5H2O and 1·py. The former readily loses the interstitial solvent to produce either a powder sample of 1 upon filtration or crystals of 1 if the solvent loss is slowed by placing the crystals of 1·2.25py·0.5H2O in diethyl ether. In contrast, 1·py exhibits higher stability toward solvent loss. The crystal packing of both solvates and of the solvent-free structure features double columns of [Fe(tpma)(xnap-bim)]2+ cations formed by efficient π-π interactions between the pyridyl groups of tpma ligands, as well as by stacks supported by π-π interactions between interdigitated naphthalene fragments of xnap-bim ligands. While both solvates show a gradual SCO between the high-spin (HS) and low-spin (LS) states of the Fe(II) ion, solvent-free complex 1 exhibits an abrupt spin transition centered at 127 K, with a narrow 2 K thermal hysteresis. Complex 1 also shows a light-induced excited spin state trapping effect, manifested as LS â HS conversion upon irradiation with white light at 5 K. The metastable HS state relaxes to the ground LS state when heated above 65 K.
ABSTRACT
Heteroleptic complexes [Fe(bpte)(bim)]X2 and [Fe(bpte)(xbim)]X2 (bpte = S,S'-bis(2-pyridylmethyl)-1,2-thioethane, bim = 2,2'-biimidazole, xbim = 1,1'-(α,α'-o-xylyl)-2,2'-biimidazole, X = ClO4-, BF4-, OTf-) were prepared by reacting the corresponding Fe(II) salts with a 1:1 mixture of the ligands. All mononuclear complexes exhibit temperature-induced spin crossover (SCO) with the onset above room temperature. The SCO is rather gradual, due to low cooperativity of interactions between the cationic complexes, as revealed by crystal structure analyses. These complexes expand the range of the recently discovered Fe(II) SCO materials with {N4S2} coordination environment.
