Koshiro Nishi

One-dimensional Spin-crossover iron(II) complexes bridged by intermolecular imidazole-pyridine NH· · · N hydrogen bonds, [Fe(HLMe)3]X2 (HLMe = (2-Methylimidazol-4-yl-methylideneamino-2-ethylpyridine; X = PF6, ClO4, BF4)

2-Methylimidazol-4-yl-methylideneamino-2-ethylpyridine (abbreviated as HL(Me)) is the 1:1 condensation product of 2-methyl-4-formylimidazole and 2-aminoethylpyridine and functions as a bidentate ligand to the iron(II) ion to produce the 3:1 complexes together with anions, [Fe(HL(Me))(3)]X(2) (X = PF(6) (1), ClO(4) (2), BF(4) (3)). The magnetic susceptibilities, differential scanning calorimetric measurements, and Mossbauer spectral measurements demonstrated that complexes 1, 2, and 3 showed a steep one-step spin crossover (SCO) between the high-spin (HS, S = 2) and low-spin (LS, S = 0) states with small thermal hysteresis. Three complexes have an isomorphous structure and are crystallized in the same monoclinic space group, C2/c, both in the HS and LS states. The iron(II) ion has the octahedral coordination geometry of a facial isomer with N(6) donor atoms of three bidentate ligands, in which an imidazole and an imine nitrogen atom per ligand participate in the formation of the coordination bond, but the pyridine nitrogen is free from coordination. The complex cation fac-[Fe(HL(Me))(3)](2+) is a chiral species with a Delta or Lambda isomer, and the adjacent Delta and Lambda isomers are linked alternately by an intermolecular imidazole-pyridine NH...N hydrogen bond to produce an achiral 1D chain. The two remaining imidazole moieties per complex are hydrogen-bonded to the anions that occupy the space among the chains. The SCO profile becomes steeper with the decrease of the anion size (73.0 A(3) for PF(6)(-), 54.4 A(3) for ClO(4)(-), and 53.4 A(3) for BF(4)(-)). The SCO transition temperature T(1/2) of the PF(6) (1), ClO(4) (2), and BF(4) (3) salts estimated from the magnetic susceptibility measurements are (T( downward arrow) = 151.8 K, T( upward arrow) = 155.3 K), (T( downward arrow) = 184.5 K, T( upward arrow) = 186.0 K), and (T( downward arrow) = 146.4 K, T( upward arrow) = 148.2 K), respectively, indicating that the T(1/2) value is not in accord with the anion size.

1D and 2D assembly structures by imidazole⋯chloride hydrogen bonds of iron(II) complexes [FeII(HLn-Pr)3]Cl·Y (HLn-Pr = 2-methylimidazol-4-yl-methylideneamino-n-propyl; Y = AsF6, BF4) and their spin states

Two Fe(II) complexes fac-[Fe(II)(HL(n-Pr))(3)]Cl·Y (Y = AsF(6) (1) and BF(4) (2)) were synthesized, where HL(n-Pr) is 2-methylimidazole-4-yl-methylideneamino-n-propyl. Each complex-cation has the same octahedral N(6) geometry coordinated by three bidentate ligands and assumes facial-isomerism, fac-[Fe(II)(HL(n-Pr))(3)](2+) with Δ- and Λ-enantiomorphs. Three imidazole groups per Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) are hydrogen-bonded to three Cl(-) ions or, from the viewpoint of the Cl(-) ion, one Cl(-) ion is hydrogen-bonded to three neighbouring fac-[Fe(II)(HL(n-Pr))(3)](2+) cations. The 3 : 3 NH···Cl(-) hydrogen bonds between Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) and Cl(-) generate two kinds of assembly structures. The directions of the 3 : 3 NH···Cl(-) hydrogen bonds and hence the resulting assembly structures are determined by the size of the anion Y, though Y is not involved into the network structure and just accommodated in the cavity. Compound 1 has a 1D ladder structure giving a larger cavity, in which the Δ- and Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) enantiomorphs are bridged by two NH···Cl(-) hydrogen bonds. Compound 2 has a 2D network structure with a net unit of a cyclic trimer of {fac-[Fe(II)(HL(n-Pr))(3)](2+)···Cl(-)}(3) giving a smaller cavity, in which Δ- or Λ-fac-[Fe(II)(HL(n-Pr))(3)](2+) species with the same chirality are linked by NH···Cl(-) hydrogen bonds to give a homochiral 2D network structure. Magnetic susceptibility and Mössbauer spectral measurements demonstrated that compound 1 showed an abrupt one-step spin crossover with 4.0 K thermal hysteresis of T(c↓) = 125.5 K and T(c↑) = 129.5 K and compound 2 showed no spin transition and stayed in the high-spin state over the 5-300 K temperature range.

A hydrogen bond motif giving a variety of supramolecular assembly structures and spin-crossover behaviors.

A series of spin-crossover (SCO) iron(II) compounds, fac-[Fe(II)(HL(R))(3)]Cl·PF(6) [R = methyl (Me, 1), ethyl (Et, 2), n-propyl (n-Pr, 3), n-butyl (n-Bu, 4), and n-pentyl (n-Pen, 5)], were synthesized, where HL(R) denotes a series of [(2-methylimidazol-4-yl)methylidene]monoalkylamines. The cations fac-[Fe(II)(HL(R))(3)](2+) and chloride anions associate through 3:3 imidazole···chloride hydrogen bonding. This hydrogen-bonding motif gives rise to a variety of assembly structures consisting of a one-dimensional ladder for 3 and 4, two kinds of two-dimensional networks for 1 and 2, and a cubane-like structure for 5. The compounds exhibit various types of SCO transitions between high-spin (S = 2) and low-spin (S = 0) states as a result of their intermolecular interactions.

Scan Rate Dependent Spin Crossover Iron(II) Complex with Two Different Relaxations and Thermal Hysteresis fac-[FeII(HLn-Pr)3]Cl·PF6 (HLn-Pr = 2-Methylimidazol-4-yl-methylideneamino-n-propyl)

Solvent-free spin crossover Fe(II) complex fac-[Fe(II)(HL(n-Pr))3]Cl·PF6 was prepared, where HL(n-Pr) denotes 2-methylimidazol-4-yl-methylideneamino-n-propyl. The magnetic susceptibility measurements at scan rate of 0.5 K min(-1) showed two successive spin transition processes consisting of the first spin transition T1 centered at 122 K (T1↑ = 127.1 K, T1↓ = 115.8 K) and the second spin transition T2 centered at ca. 105 K (T2↑ = 115.8 K, T2↓ = 97.2 K). The magnetic susceptibility measurements at the scan rate of 2.0, 1.0, 0.5, 0.25, and 0.1 K min(-1) showed two scan speed dependent spin transitions, while the Mössbauer spectra detected only the first spin transition T1. The crystal structures were determined at 160, 143, 120, 110, 95 K in the cooling mode, and 110, 120, and 130 K in the warming mode so as to follow the spin transition process of high-spin HS → HS(T1) → HS(T2) → low-spin LS → LS(T2) → LS(T1) → HS. The crystal structures at all temperatures have a triclinic space group P1̅ with Z = 2. The complex-cation has an octahedral N6 coordination geometry with three bidentate ligands and assume a facial-isomer with Δ- and Λ-enantimorphs. Three imidazole groups of fac-[Fe(II)(HL(n-Pr))3](2+) are hydrogen-bonded to three Cl(-) ions. The 3:3 NH(imidazole)···Cl(-) hydrogen-bonds form a stepwise ladder assembly structure, which is maintained during the spin transition process. The spin transition process is related to the structural changes of the FeN6 coordination environment, the order-disorder of PF6(-) anion, and the conformation change of n-propyl groups. The Fe-N bond distance in the HS state is longer by 0.2 Å than that in the LS state. Disorder of PF6(-) anion is not observed in the LS state but in the HS state. The conformational changes of n-propyl groups are found in the spin transition processes except for HS → HS(T1) → HS(T2).