Iron(II) complexes of 2,6-bis(imidazo[1,2-a]pyridin-2-yl)pyridine and related ligands with annelated distal heterocyclic donors.

Following a published synthesis of 2,6-bis(imidazo[1,2-a]pyridin-2-yl)pyridine (L1), treatment of α,α'-dibromo-2,6-diacetylpyridine with 2 equiv. 2-aminopyrimidine or 2-aminoquinoline in refluxing acetonitrile respectively gives 2,6-bis(imidazo[1,2-a]pyrimidin-2-yl)pyridine (L2) and 2,6-bis(imidazo[1,2-a]quinolin-2-yl)pyridine (L3). Solvated crystals of [Fe(L1)2][BF4]2 (1[BF4]2) and [Fe(L2)2][BF4]2 (2[BF4]2) are mostly high-spin, although one solvate of 1[BF4]2 undergoes thermal spin-crossover on cooling. The iron coordination geometry is consistently distorted in crystals of 2[BF4]2 which may reflect the influence of intramolecular, inter-ligand N⋯π interactions on the molecular conformation. Only 1 : 1 Fe : L3 complexes were observed in solution, or isolated in the solid state; a crystal structure of [FeBr(py)2L3]Br·0.5H2O (py = pyridine) is presented. A solvate crystal structure of high-spin [Fe(L4)2][BF4]2 (L4 = 2,6-di{quinolin-2-yl}pyridine; 4[BF4]2) is also described, which exhibits a highly distorted six-coordinate geometry with a helical ligand conformation. The iron(II) complexes are high-spin in solution at room temperature, but 1[BF4]2 and 2[BF4]2 undergo thermal spin-crossover equilibria on cooling. All the compounds exhibit a ligand-based emission in solution at room temperature. Gas phase DFT calculations mostly reproduce the spin state properties of the complexes, but show small anomalies attributed to intramolecular, inter-ligand dispersion interactions in the sterically crowded molecules.

Ligand-Directed Metalation of a Gold Pyrazolate Cluster.

Solid "[AuL]" (HL = 3-[pyrid-2-yl]-5-tertbutyl-1H-pyrazole) can be crystallized as cyclic [Au3(µ-L)3] and [Au4(µ-L)4] clusters from different solvents. The crystalline tetramer contains a square Au4 core with an HT:TH:TH:HT arrangement of ligand substituents, which preorganizes the cluster to chelate to additional metal ions via its pendant pyridyl groups. The addition of 0.5 equiv of AgBF4 to [AuL] yields [Ag2Au4(µ3-L)4][BF4]2, where two edges of the Au4 square are spanned by Ag+ ions via metallophilic Ag···Au contacts. Treatment of [AuL] with [Cu(NCMe)4]PF6 affords the metalloligand helicate [Cu2Au2(µ-L)4][PF6]2, via oxidation of the copper and partial fragmentation of the cluster.

Di-Iron(II) [2+2] Helicates of Bis-(Dipyrazolylpyridine) Ligands: The Influence of the Ligand Linker Group on Spin State Properties.

Four bis[2-{pyrazol-1-yl}-6-{pyrazol-3-yl}pyridine] ligands have been synthesized, with butane-1,4-diyl (L1 ), pyrid-2,6-diyl (L2 ), benzene-1,2-dimethylenyl (L3 ) and propane-1,3-diyl (L4 ) linkers between the tridentate metal-binding domains. L1 and L2 form [Fe2 (µ-L)2 ]X4 (X- =BF4 - or ClO4 - ) helicate complexes when treated with the appropriate iron(II) precursor. Solvate crystals of [Fe2 (µ-L1 )2 ][BF4 ]4 exhibit three different helicate conformations, which differ in the torsions of their butanediyl linker groups. The solvates exhibit gradual thermal spin-crossover, with examples of stepwise switching and partial spin-crossover to a low-temperature mixed-spin form. Salts of [Fe2 (µ-L2 )2 ]4+ are high-spin, which reflects their highly twisted iron coordination geometry. The composition and dynamics of assembly structures formed by iron(II) with L1 -L3 vary with the ligand linker group, by mass spectrometry and 1 H NMR spectroscopy. Gas-phase DFT calculations imply the butanediyl linker conformation in [Fe2 (µ-L1 )2 ]4+ influences its spin state properties, but show anomalies attributed to intramolecular electrostatic repulsion between the iron atoms.

Iron(II) Complexes of 4-(Alkyldisulfanyl)-2,6-di(pyrazolyl)pyridine Derivatives. Correlation of Spin-Crossover Cooperativity with Molecular Structure Following Single-Crystal-to-Single-Crystal Desolvation.

The complex salts [Fe(L 1)2]X2 (1X 2 ; L 1 = 4-(isopropyldisulfanyl)-2,6-bis(pyrazolyl)pyridine; X- = BF4 -, ClO4 -) form solvated crystals from common organic solvents. Crystals of 1X 2 ·Me2CO show abrupt spin transitions near 160 K, with up to 22 K thermal hysteresis. 1X 2 ·Me2CO cocrystallizes with other, less cooperative acetone solvates, which all transform into the same solvent-free materials 1X 2 ·sf upon exposure to air, or mild heating. Conversion of 1X 2 ·Me2CO to 1X 2 ·sf proceeds in a single-crystal to single-crystal fashion. 1X 2 ·sf are not isomorphous with the acetone solvates, and exhibit abrupt spin transitions at low temperature with hysteresis loops of 30-38 K (X- = BF4 -) and 10-20 K (X- = ClO4 -), depending on the measurement method. Interestingly, the desolvation has an opposite effect on the SCO temperature and hysteresis in the two salts. The hysteretic spin transitions in 1X 2 ·Me2CO and 1X 2 ·sf do not involve a crystallographic phase change but are accompanied by a significant rearrangement of the metal coordination sphere. Other solvates 1X 2 ·MeNO2, 1X 2 ·MeCN, and 1X 2 ·H2O are mostly isomorphous with each other and show more gradual spin-crossover equilibria near room temperature. All three of these lattice types have similar unit cell dimensions and contain cations associated into chains through pairwise, intermolecular S···π interactions. Polycrystalline [Fe(L 2)2][BF4]2·MeNO2 (2[BF 4 ] 2 ·MeNO2; L 2 = 4-(methyldisulfanyl)-2,6-bis(pyrazolyl)pyridine) shows an abrupt spin transition just above room temperature, with an unsymmetrical and structured hysteresis loop, whose main features are reversible upon repeated thermal scanning.

Structures and Spin States of Iron(II) Complexes of Isomeric 2,6-Di(1,2,3-triazolyl)pyridine Ligands.

Iron(II) complex salts of 2,6-di(1,2,3-triazol-1-yl)pyridine (L1) are unexpectedly unstable in undried solvent. This is explained by the isolation of [Fe(L1)4(H2O)2][ClO4]2 and [Fe(NCS)2(L1)2(H2O)2]·L1, containing L1 bound as a monodentate ligand rather than in the expected tridentate fashion. These complexes associate into 44 grid structures through O-H···N hydrogen bonding; a solvate of a related 44 coordination framework, catena-[Cu(µ-L1)2(H2O)2][BF4]2, is also presented. The isomeric ligands 2,6-di(1,2,3-triazol-2-yl)pyridine (L2) and 2,6-di(1H-1,2,3-triazol-4-yl)pyridine (L3) bind to iron(II) in a more typical tridentate fashion. Solvates of [Fe(L3)2][ClO4]2 are low-spin and diamagnetic in the solid state and in solution, while [Fe(L2)2][ClO4]2 and [Co(L3)2][BF4]2 are fully high-spin. Treatment of L3 with methyl iodide affords 2,6-di(2-methyl-1,2,3-triazol-4-yl)pyridine (L4) and 2-(1-methyl-1,2,3-triazol-4-yl)-6-(2-methyl-1,2,3-triazol-4-yl)pyridine (L5). While salts of [Fe(L5)2]2+ are low-spin in the solid state, [Fe(L4)2][ClO4]2·H2O is high-spin, and [Fe(L4)2][ClO4]2·3MeNO2 exhibits a hysteretic spin transition to 50% completeness at T1/2 = 128 K (ΔT1/2 = 6 K). This transition proceeds via a symmetry-breaking phase transition to an unusual low-temperature phase containing three unique cation sites with high-spin, low-spin, and 1:1 mixed-spin populations. The unusual distribution of the spin states in the low-temperature phase reflects "spin-state frustration" of the mixed-spin cation site by an equal number of high-spin and low-spin nearest neighbors. Gas-phase density functional theory calculations reproduce the spin-state preferences of these and some related complexes. These highlight the interplay between the σ-basicity and π-acidity of the heterocyclic donors in this ligand type, which have opposing influences on the molecular ligand field. The Brønsted basicities of L1-L3 are very sensitive to the linkage isomerism of their triazolyl donors, which explains why their iron complex spin states show more variation than the better-known iron(II)/2,6-dipyrazolylpyridine system.

The number and shape of lattice solvent molecules controls spin-crossover in an isomorphous series of crystalline solvate salts.

Crystals of [FeL2][BF4]2·nMeCN (L = N-(2,6-di{pyrazol-1-yl}pyrid-4-yl)acetamide; n = 1 or 2) and [FeL2][ClO4]2·MeCN are isomorphous. When n = 1 the compounds exhibit an abrupt, hysteretic spin-transition below 200 K, but when n = 2 the material remains high-spin on cooling. [FeL2]X2·EtCN (X- = BF4- or ClO4-) are isomorphous with the MeCN solvates and undergo their spin-transition at almost the same temperature. However this now occurs in two-steps via a re-entrant mixed-spin intermediate phase, which correlates with crystallographic ordering of the bent propionitrile molecule.

The flexibility of long chain substituents influences spin-crossover in isomorphous lipid bilayer crystals.

[Fe(bpp)2][BF4]2 (bpp = 2,6-di{pyrazol-1-yl}pyridine) derivatives with a bent geometry of hexadec-1-ynyl or hexadecyl pyrazole substituents are isomorphous, and high-spin at room temperature. However, only the latter compound undergoes an abrupt, stepwise spin-transition on cooling. This may reflect the different conformational flexibilities of their long chain substituents.

Influence of ligand substituent conformation on the spin state of an iron(II)/di(pyrazol-1-yl)pyridine complex.

The temperature of the solution-phase spin-crossover equilibrium in iron(ii) complexes of 4-alkylsulfanyl-2,6-di{pyrazol-1-yl}pyridine (bppSR) complexes depends strongly on the alkylsulfanyl substituent. DFT calculations imply this reflects the conformation of the alkylsulfanyl groups, which lie perpendicular to the heterocyclic ligand donors in [Fe(bppStBu)2]2+ but are oriented co-planar with the ligand core for smaller SR substituents.

Structural Transformations and Spin-Crossover in [FeL2 ]2+ Salts (L=4-{tert-Butylsulfanyl}-2,6-di{pyrazol-1-yl}pyridine): The Influence of Bulky Ligand Substituents.

4-(tert-Butylsulfanyl)-2,6-di(pyrazol-1-yl)pyridine (L) was obtained in low yield from a one-pot reaction of 2,4,6-trifluoropyridine with 2-methylpropane-2-thiolate and sodium pyrazolate in a 1:1:2 ratio. The materials [FeL2 ][BF4 ]2 ⋅solv (1[BF4 ]2 ⋅solv) and [FeL2 ][ClO4 ]2 ⋅solv (1[ClO4 ]2 ⋅solv; solv=MeNO2 , MeCN or Me2 CO) exhibit a variety of structures and spin-state behaviors including thermal spin-crossover (SCO). Solvent loss on heating 1[BF4 ]2 ⋅x MeNO2 (x≈2.3) occurs in two steps. The intermediate phase exhibits hysteretic SCO around 250 K, involving a "reverse-SCO" step in its warming cycle at a scan rate of 5 K min-1 . The reverse-SCO is not observed in a slower 1 K min-1 measurement, however, confirming its kinetic nature. The final product [FeL2 ][BF4 ]2 ⋅0.75 MeNO2 was crystallographically characterized, and shows abrupt but incomplete SCO at 172 K which correlates with disorder of an L ligand. The asymmetric unit of 1[BF4 ]2 ⋅y Me2 CO (y≈1.6) contains five unique complex molecules, four of which undergo gradual SCO in at least two discrete steps. Low-spin 1[ClO4 ]2 ⋅0.5 Me2 CO is not isostructural with its BF4 - congener, and undergoes single-crystal-to-single-crystal solvent loss with a tripling of the crystallographic unit cell volume, while retaining the P 1 ‾ space group. Three other solvate salts undergo gradual thermal SCO. Two of these are isomorphous at room temperature, but transform to different low-temperature phases when the materials are fully low-spin.

Modulating the Magnetic Properties of Copper(II)/Nitroxyl Heterospin Complexes by Suppression of the Jahn-Teller Distortion.

A series of six-coordinate [Cu(L)L1][BF4]2 (L1 = 2,6-bis{1-oxyl-4,4,5,5-tetramethyl-4,5-dihydro-1H-imidazol-2-yl}pyridine) complexes are reported. Ferromagnetic coupling between the Cu and L1 ligand spins is enhanced by an L coligand with distal methyl substituents, which is attributed to a sterically induced suppression of its Jahn-Teller distortion.

Elucidating the Structural Chemistry of a Hysteretic Iron(II) Spin-Crossover Compound From its Copper(II) and Zinc(II) Congeners.

Annealing [FeL2 ][BF4 ]2 ⋅2 H2 O (L=2,6-bis-[5-methyl-1H-pyrazol-3-yl]pyridine) affords an anhydrous material, which undergoes a spin transition at T1/2 =205 K with a 65 K thermal hysteresis loop. This occurs through a sequence of phase changes, which were monitored by powder diffraction in an earlier study. [CuL2 ][BF4 ]2 ⋅2 H2 O and [ZnL2 ][BF4 ]2 ⋅2 H2 O are not perfectly isostructural but, unlike the iron compound, they undergo single-crystal-to-single-crystal dehydration upon annealing. All the annealed compounds initially adopt the same tetragonal phase but undergo a phase change near room temperature upon re-cooling. The low-temperature phase of [CuL2 ][BF4 ]2 involves ordering of its Jahn-Teller distortion, to a monoclinic lattice with three unique cation sites. The zinc compound adopts a different, triclinic low-temperature phase with significant twisting of its coordination sphere, which unexpectedly becomes more pronounced as the crystal is cooled. Synchrotron powder diffraction data confirm that the structural changes in the anhydrous zinc complex are reproduced in the high-spin iron compound, before the onset of spin-crossover. This will contribute to the wide hysteresis in the spin transition of the iron complex. EPR spectra of copper-doped [Fe0.97 Cu0.03 L2 ][BF4 ]2 imply its low-spin phase contains two distinct cation environments in a 2:1 ratio.

Molecular squares, coordination polymers and mononuclear complexes supported by 2,4-dipyrazolyl-6H-1,3,5-triazine and 4,6-dipyrazolylpyrimidine ligands.

The Fe[BF4]2 complex of 2,4-di(pyrazol-1-yl)-6H-1,3,5-triazine (L1) is a high-spin molecular square, [{Fe(L1)}4(µ-L1)4][BF4]8, whose crystals also contain the unusual HPzBF3 (HPz = pyrazole) adduct. Three other 2,4-di(pyrazol-1-yl)-6H-1,3,5-triazine derivatives with different pyrazole substituents (L2-L4) are unstable in the presence of first row transition ions, but form mononuclear, polymeric or molecular square complexes with silver(i). Most of these compounds involve bis-bidentate di(pyrazolyl)triazine coordination, which is unusual for that class of ligand, and the molecular squares encapsulate one or two BF4-, ClO4- or SbF6- ions through combinations of anionπ, AgX and/or C-HX (X = O or F) interactions. Treatment of Fe[NCS]2 or Fe[NCSe]2 with 4,6-di(pyrazol-1-yl)-2H-pyrimidine (L5) or its 2-methyl and 2-amino derivatives (L6 and L7) yields mononuclear [Fe(NCE)2L2] and/or the 1D coordination polymers catena-[Fe(NCE)2(µ-L)] (E = S or Se, L = L5-L7). Alcohol solvates of isomorphous [Fe(NCS)2L2] and [Fe(NCSe)2L2] compounds show different patterns of intermolecular hydrogen bonding, reflecting the acceptor properties of the anion ligands. These iron compounds are all high-spin, although annealing solvated crystals of [Fe(NCSe)2(L5)2] affords a new phase exhibiting an abrupt, low-temperature spin transition. Catena-[Fe(H2O)2(µ-L5)][ClO4]2 is a coordination polymer of alternating cis and trans iron centres.

Supramolecular Iron Metallocubanes Exhibiting Site-Selective Thermal and Light-Induced Spin-Crossover.

Treatment of Fe[BF4]2·6H2O with 4,6-di(pyrazol-1-yl)-1H-pyrimid-2-one (HL1) or 4,6-di(4-methylpyrazol-1-yl)-1H-pyrimid-2-one (HL2) affords solvated crystals of [{FeIII(OH2)6}⊂FeII8(µ-L)12][BF4]7 (1, HL = HL1; 2, HL = HL2). The centrosymmetric complexes contain a cubic arrangement of iron(II) centers, with bis-bidentate [L]- ligands bridging the edges of the cube. The encapsulated [Fe(OH2)6]3+ moiety templates the assembly through 12 O-H···O hydrogen bonds to the [L]- hydroxylate groups. All four unique iron(II) ions in the cages are crystallographically high-spin at 250 K, but they undergo a gradual high → low spin-crossover on cooling, which is predominantly centered on one iron(II) site and its symmetry-related congener. This was confirmed by magnetic susceptibility data, light-induced excited spin state trapping (LIESST) effect measurements, and, for 1, Mössbauer spectroscopy and diffuse reflectance data. The clusters are stable in MeCN solution, and 1 remains high-spin above 240 K in that solvent. The cubane assembly was not obtained from reactions using other iron(II) salts or 4,6-di(pyrazol-1-yl)pyrimidine ligands, highlighting the importance of hydrogen bonding in templating the cubane assembly.

Relationship between the Molecular Structure and Switching Temperature in a Library of Spin-Crossover Molecular Materials.

Structure-function relationships relating the spin-crossover (SCO) midpoint temperature (T1/2) in the solid state are surveyed for 43 members of the iron(II) dipyrazolylpyridine family of SCO compounds. The difference between T1/2 in the solid state and in solution [ΔT(latt)] is proposed as a measure of the lattice contribution to the transition temperature. Negative linear correlations between the SCO temperature and the magnitude of the rearrangement of the coordination sphere during SCO are evident among isostructural or near-isostructural subsets of compounds; that is, a larger change in the molecular structure during SCO stabilizes the high-spin state of a material. Improved correlations are often obtained when ΔT(latt), rather than the raw T1/2 value, is considered as the measure of the SCO temperature. Different lattice types show different tendencies to stabilize the high-spin or low-spin state of the molecules they contain, which correlates with the structural changes that most influence ΔT(latt) in each case. These relationships are mostly unaffected by the SCO cooperativity in the compounds or by the involvement of any crystallographic phase changes. One or two materials within each subset are outliers in some or all of these correlations, however, which, in some cases, can be attributed to small differences in their ligand geometry or unusual phase behavior during SCO. A reinvestigation of the structural chemistry of [Fe(3-bpp)2][NCS]2·nH2O [3-bpp = bis(1H-pyrazol-3-yl)pyridine; n = 0 or 2], undertaken as part of this study, is also presented.

Giant Barocaloric Effect at the Spin Crossover Transition of a Molecular Crystal.

The first experimental evidence for a giant, conventional barocaloric effect (BCE) associated with a pressure-driven spin crossover transition near room temperature is provided. Magnetometry, neutron scattering, and calorimetry are used to explore the pressure dependence of the SCO phase transition in polycrystalline samples of protonated and partially deuterated [FeL2 ][BF4 ]2 [L = 2,6-di(pyrazol-1-yl)pyridine] at applied pressures of up to 120 MPa (1200 bar). The data indicate that, for a pressure change of only 0-300 bar (0-30 MPa), an adiabatic temperature change of 3 K is observed at 262 K or 257 K in the protonated and deuterated materials, respectively. This BCE is equivalent to the magnetocaloric effect (MCE) observed in gadolinium in a magnetic field change of 0-1 Tesla. The work confirms recent predictions that giant, conventional BCEs will be found in a wide range of SCO compounds.

2,6-Bis(pyrazol-1-yl)pyridine-4-carboxylate Esters with Alkyl Chain Substituents and Their Iron(II) Complexes.

Two series of 4-(alkoxyphenyl) 2,6-bis{pyrazol-1-yl}pyridine-4-carboxyate (L3R) or alkyl 2,6-bis{pyrazol-1-yl}pyridine-4-carboxyate (L4R) esters have been synthesized and complexed to iron(II), where R = C nH2 n+1 ( n = 6, 12, 14, 16, 18); two other derivatives related to L3R are also reported. While the solid [Fe(L4R)2][BF4]2 compounds are isostructural by powder diffraction and show similar spin state behaviors, the [Fe(L3R)2][BF4]2 series shows more varied structures and magnetic properties. This was confirmed by solvated crystal structures of [Fe(L3R)2][BF4]2 with n = 6, 14, 16, which all adopt the P1̅ space group but show significantly different side-chain conformations and/or crystal packing. The solid complexes are mostly low spin at room temperature, with many exhibiting the onset of thermal spin crossover (SCO) upon warming. Heating the complexes with n ≥ 14 significantly above their SCO temperature transforms them irreversibly into a predominantly high spin state, which is accompanied by structure changes and loss of crystallinity by powder diffraction. These transformations do not coincide with lattice solvent loss and may reflect melting and refreezing of their alkyl chain conformations during the thermal cycle. Four of the complexes exhibit SCO in CD3CN solution with T1/2 = 273-277 K, which is apparently unaffected by their alkyl chain substituents.

An Incomplete Spin Transition Associated with a Z'=1→Z'=24†Crystallographic Symmetry Breaking.

Crystalline [FeL2 ][BF4 ]2 ⋅Me2 CO (L=N-[2,6-di{pyrazol-1-yl}pyrid-4-yl]acetamide) is high-spin at room temperature, and undergoes an abrupt, hysteretic spin-crossover at T1/2 =137 K (ΔT1/2 =14 K) that proceeds to about 50 % completeness. This is associated with a crystallographic phase transition, from phase 1 (P21 /c, Z=4) to phase 2 (P21 , Z=48). The cations associate into chains in the crystal through weak intermolecular π⋅⋅⋅π interactions. Phase 2 contains a mixture of high-spin and low-spin molecules, which are grouped into triads along these chains. The perchlorate salt [FeL2 ][ClO4 ]2 ⋅Me2 CO also adopts phase 1 at room temperature but undergoes a different phase transition near 135 K to phase 3 (P21 /c, Z=8) without a change in spin state.

The role of symmetry breaking in the structural trapping of light-induced excited spin states.

Light-Induced Excited Spin State Trapping (LIESST) data are reported for seven isostructural solvate salts from the iron(ii)/2,6-di(pyrazol-1-yl)pyridine family. A complicated relationship between their spin-crossover T1/2 and T(LIESST) values may reflect low-temperature thermal and light-induced symmetry breaking, which is shown by one of the compounds but not by two others.

Iron(II) Complexes of 2,4-Dipyrazolyl-1,3,5-triazine Derivatives-The Influence of Ligand Geometry on Metal Ion Spin State.

Seven [FeL2][BF4]2 complex salts were prepared, where L is a 6-substituted 2,4-di(pyrazol-1-yl)-1,3,5-triazine (bpt) derivative. The complexes are all crystallographically high-spin, and exhibit significant distortions from an ideal D2d-symmetric coordination geometry. In one case, an unusual type of metal ion disorder was observed among a cubic array of ligands in the crystal lattice. The complexes are also high-spin between 3 and 300 K in the solid state and, where measured, between 239 and 333 K in CD3CN solution. This result is unexpected, since homoleptic iron(II) complexes of related 2,6-di(pyrazol-1-yl)pyridine, 2,6-di(pyrazol-1-yl)pyrazine, and 2,6-di(pyrazol-1-yl)pyrimidine derivatives often exhibit thermal spin-crossover behavior. Gas-phase density functional theory calculations confirm the high-spin form of [Fe(bpt)2]2+ and its derivatives is stabilized relative to iron(II) complexes of the other ligand types. This reflects a weaker Fe/pyrazolyl σ-bonding interaction, which we attribute to a small narrowing of the chelate ligand bite angle associated with the geometry of the 1,3,5-triazinyl ring. Hence, the high-spin state of [Fe(bpt)2]2+ centers does not reflect the electronic properties of its heterocyclic ligand donors but is imposed by the bpt ligand conformation. A high-spin homoleptic iron(III) complex of one of the bpt derivatives was also synthesized.

Spin States of Homochiral and Heterochiral Isomers of [Fe(PyBox)2 ]2+ Derivatives.

The following iron(II) complexes of 2,6-bis(oxazolinyl)pyridine (PyBox; LH ) derivatives are reported: [Fe(LH )2 ][ClO4 ]2 (1); [Fe((R)-LMe )2 ][ClO4 ]2 ((R)-2; LMe =2,6-bis{4-methyloxazolinyl}pyridine); [Fe((R)-LPh )2 ][ClO4 ]2 ((R)-3) and [Fe((R)-LPh )((S)-LPh )][ClO4 ]2 ((RS)-3; LPh =2,6-bis{4-phenyloxazolinyl}pyridine); and [Fe((R)-LiPr )2 ][ClO4 ]2 ((R)-4) and [Fe((R)-LiPr )((S)-LiPr )][ClO4 ]2 ((RS)-4; LiPr =2,6-bis{4-isopropyloxazolinyl}pyridine). Solid (R)-3⋅MeNO2 exhibits an unusual very gradual, but discontinuous thermal spin-crossover with an approximate T1/2 of 350 K. The discontinuity around 240 K lies well below T1/2 , and is unconnected to a crystallographic phase change occurring at 170 K. Rather, it can be correlated with a gradual ordering of the ligand conformation as the temperature is raised. The other solid compounds either exhibit spin-crossover above room temperature (1 and (RS)-3), or remain high-spin between 5-300 K [(R)-2, (R)-4 and (RS)-4]. Homochiral (R)-3 and (R)-4 exhibit more twisted ligand conformations and coordination geometries than their heterochiral isomers, which can be attributed to steric clashes between ligand substituents [(R)-3]; or, between the isopropyl substituents of one ligand and the backbone of the other ((R)-4). In solution, (RS)-3 retains its structural integrity but (RS)-4 undergoes significant racemization through ligand redistribution by 1 H NMR. (R)-4 and (RS)-4 remain high-spin in solution, whereas the other compounds all undergo spin-crossover equilibria. Importantly, T1/2 for (R)-3 (244 K) is 34 K lower than for (RS)-3 (278 K) in CD3 CN, which is the first demonstration of chiral discrimination between metal ion spin states in a molecular complex.