Fe-N Bond Lengths Research Articles

Spin-Crossover in a Pseudo-tetrahedral Bis(formazanate) Iron Complex.

Spin-crossover in a pseudo-tetrahedral bis(formazanate) iron(II) complex (1) is described. Structural, magnetic, and spectroscopic analyses indicate that this compound undergoes thermal switching between an S=0 and an S=2 state, which is very rare in four-coordinate complexes. The transition to the high-spin state is accompanied by an increase in Fe-N bond lengths and a concomitant contraction of intraligand N-N bonds. The latter suggests that stabilization of the low-spin state is due to the π-acceptor properties of the ligand. One-electron reduction of 1 leads to the formation of the corresponding anion, which contains a low-spin (S=1/2) Fe(I) center. The findings are rationalized by electronic structure calculations using density functional theory.

Insight into the reactivity and electronic structure of dinuclear dinitrosyl iron complexes.

A combination of N/S/Fe K-edge X-ray absorption spectroscopy (XAS), X-ray diffraction data, and density functional theory (DFT) calculations provides an efficient way to unambiguously delineate the electronic structures and bonding characters of Fe-S, N-O, and Fe-N bonds among the direduced-form Roussin's red ester (RRE) [Fe2(μ-SPh)2(NO)4](2-)(1) with {Fe(NO)2}(10)-{Fe(NO)2}(10) core, the reduced-form RRE [Fe2(μ-SPh)2(NO)4](-)(3) with {Fe(NO)2}(9)-{Fe(NO)2}(10) core, and RRE [Fe2(μ-SPh)2(NO)4] (4) with {Fe(NO)2}(9)-{Fe(NO)2}(9) core. The major contributions of highest occupied molecular orbital (HOMO) 113α/β in complex 1 is related to the antibonding character between Fe(d) and Fe(d), Fe(d), and S atoms, and bonding character between Fe(d) and NO(π*). The effective nuclear charge (Zeff) of Fe site can be increased by removing electrons from HOMO to shorten the distances of Fe···Fe and Fe-S from 1 to 3 to 4 or, in contrast, to increase the Fe-N bond lengths from 1 to 3 to 4. The higher IR νNO stretching frequencies (1761, 1720 cm(-1) (4), 1680, 1665 cm(-1) (3), and 1646, 1611, 1603 cm(-1) (1)) associated with the higher transition energy of N1s →σ*(NO) (412.6 eV (4), 412.3 eV (3), and 412.2 eV (1)) and the higher Zeff of Fe derived from the transition energy of Fe1s → Fe3d (7113.8 eV (4), 7113.5 eV (3), and 7113.3 eV (1)) indicate that the N-O bond distances of these complexes are in the order of 1 > 3 > 4. The N/S/Fe K-edge XAS spectra as well as DFT computations reveal the reduction of complex 4 yielding complex 3 occurs at Fe, S, and NO; in contrast, reduction mainly occurs at Fe site from complex 3 to complex 1.

Spin crossover in Fe(II) and Co(II) complexes with the same click-derived tripodal ligand.

The complexes [Fe(tbta)2](BF4)2·2EtOH (1), [Fe(tbta)2](BF4)2·2CH3CN (2), [Fe(tbta)2](BF4)2·2CHCl3 (3), and [Fe(tbta)2](BF4)2 (4) were synthesized from the respective metal salts and the click-derived tripodal ligand tris[(1-benzyl-1H-1,2,3-triazol-4-yl)methyl]amine (tbta). Structural characterization of these complexes (at 100 or 133 K) revealed Fe-N bond lengths for the solvent containing compounds 1-3 that are typical of a high spin (HS) Fe(II) complex. In contrast, the solvent-free compound 4 show Fe-N bond lengths that are characteristic of a low spin (LS) Fe(II) state. The Fe center in all complexes is bound to two triazole and one amine N atom from each tbta ligand, with the third triazole arm remaining uncoordinated. The benzyl substituents of the uncoordinated triazole arms and the triazole rings engage in strong intermolecular and intramolecular noncovalent interactions. These interactions are missing in the solvent containing molecules 1, 2, and 3, where the solvent molecules occupy positions that hinder these noncovalent interactions. The solvent-free complex (4) displays spin crossover (SCO) with a spin transition temperature T1/2 near room temperature, as revealed by superconducting quantum interference device (SQUID) magnetometric and Mössbauer spectroscopic measurements. The complexes 1, 2, and 3 remain HS throughout the investigated temperature range. Different torsion angles at the metal centers, which are influenced by the noncovalent interactions, are likely responsible for the differences in the magnetic behavior of these complexes. The corresponding solvent-free Co(II) complex (6) is also LS at lower temperatures and displays SCO with a temperature T1/2 near room temperature. Theoretical calculations at molecular and periodic DFT-D3 levels for 1-4 qualitatively reproduce the experimental findings, and corroborate the importance of intermolecular and intramolecular noncovalent interactions for the magnetic properties of these complexes. The present work thus represents rare examples of SCO complexes where the use of identical ligand sets produces SCO in Fe(II) as well as Co(II) complexes.

Manipulation of spin state of iron porphyrin by chemisorption on magnetic substrates

One of the key factors behind the rapid evolution of molecular spintronics is the efficient realization of spin manipulation of organic molecules with a magnetic center. The spin state of such molecules may depend crucially on the interaction with the substrate on which they are adsorbed. In this paper we demonstrate, using ab initio density functional calculations, that the stabilization of a high spin state of an iron porphyrin (FeP) molecule can be achieved via chemisorption on magnetic substrates of different species and orientations, viz., Co(001), Ni(001), Ni(110), and Ni(111). The signature of chemisorption of FeP on magnetic substrates is evident from broad features in N $K$ x-ray absorption (XA) and Fe ${L}_{2,3}$ x-ray magnetic circular dichroism (XMCD) measurements. Our theoretical calculations show that the strong covalent interaction with the substrate increases Fe-N bond lengths in FeP and hence a switching to a high spin state ($S=2$) from an intermediate spin state ($S=1$) is achieved. Due to chemisorption, ferromagnetic exchange interaction is established through a direct exchange between Fe and substrate magnetic atoms as well as through an indirect exchange via the N atoms in FeP. The mechanism of exchange interaction is further analyzed by considering structural models constructed from ab initio calculations. Also, it is found that the exchange interaction between Fe in FeP and a Ni substrate is almost 4 times smaller than with a Co substrate. Finally, we illustrate the possibility of detecting a change in the molecular spin state by XMCD, Raman spectroscopy, and spin-polarized scanning tunneling microscopy.

Tris(1,10-phenanthroline-κ2N,N′)iron(II) bis(1,1,3,3-tetracyano-2-ethoxypropenide) hemihydrate

In the title hydrated mol­ecular salt, [Fe(C12H8N2)3](C9H5N4O)2·0.5H2O, the water mol­ecule site is half-occupied. The Fe—N bond lengths within the octa­hedral tris-chelate [Fe(phen)3]2+ ion (phen is 1,10-phenantroline) are indicative of a low-spin d 6 electronic configuration for the metal ion. The C—N, C—C and C—O bond lengths in the polynitrile anions indicate extensive electronic delocalization. In the crystal, the components are linked through O—H⋯N hydrogen bonds, forming [100] chains, as well as through Coulombic inter­actions.

Evidence of decisive effect of crystal-field splitting in spin-state transition

Based on the first-principle calculations for 3D Hofmann-like spin-crossover (SCO) compound [Fe(C4H4N2){Pt(CN)4}], the discrepancy of transition mechanism is clarified with quantitatively distinguishable evidence of second order phase transition. It shows that the stretch around 0.2 A of Fe-N bond length leads to the continuous structure expansion, as the energy splitting ΔEHL between low-spin and high-spin states reduces from 2.554 2 eV to −0.327 8 eV, and the crystal-field splitting (CFS) is reduced from 1.845 8 eV to 0.420 8 eV meanwhile. A physics image relating the calculations results with CFS in the frame of ligand-field theory is presented, which manifests that CFS is a necessary parameter to be introduced directly in the theory of spinstate transition.

Dicarbonyl(hexamethylene-1,3,5,7-tetramine-κN1)(η5-pentamethylcyclopentadienyl)iron(II) tetrafluoridoborate

In the title compound, [Fe(C10H15)(C6H12N4)(CO)2]BF4, the arrangement around the FeII atom corresponds to a three-legged piano stool. The penta­methyl­cyclo­penta­dienyl (Cp*) ligand occupies three coordination sites, while two CO ligands and one N atom of the hexa­methyl­ene­tetra­mine ligand occupy the remaining coordination sites, completing a pseudo-octahedral geometry. Both the complex cation and the BF4 − anion reside on crystallographic mirror planes. The Fe—N bond length is 2.069 (2) and the Fe—Cp*(centroid) distance is 1.7452 (3) Å.

X-ray study of the third polymorphic structure of μ-oxo-bis[(octaethylporphinato)iron(III)]: [(OEPFe)2O)

Exposure of a dichloromethane solution of [OEPFeIIICl], where OEP is the dianion of octaethylporphyrin, to dioxygen results in its transformation into the μ-oxo bridged compound [(OEPFe)2O)]. The structure of [(OEPFe)2O)] is determined by X-ray diffraction analysis. It contains binuclear centrosymmetric [(OEPFe)2O]. The Fe atom is five-coordinated to four N atoms of the porphyrin ring and to one bridging O atom. The compound is characterized by an average Fe-N bond length of 2.096 A. The Fe-O bond distance is 1.7739(12) A, the Fe-O-Fe bond angle is 180.0° and the two porphyrin rings are parallel. Crystal data: triclinic crystal system, a = 10.915(4) A, b = 12.951(4) A, c = 13.403(4) A, α = 118.06(1)°, β = 100.33(1)°, Γ = 102.43°, \(P\bar 1\) space group, V = 1144.5(1) A3, Z = 1.

Is histidine dissociation a critical component of the NO/H-NOX signaling mechanism? Insights from X-ray absorption spectroscopy.

The H-NOX (Heme-Nitric oxide/OXygen binding) family of diatomic gas sensing hemoproteins has attracted great interest. Soluble guanylate cyclase (sGC), the well-characterized eukaryotic nitric oxide (NO) sensor is an H-NOX family member. When NO binds sGC at the ferrous histidine-ligated protoporphyrin-IX, the proximal histidine ligand dissociates, resulting in a 5-coordinate (5c) complex; formation of this 5c complex is viewed as necessary for activation of sGC. Characterization of other H-NOX family members has revealed that while most also bind NO in a 5c complex, some bind NO in a 6-coordinate (6c) complex or as a 5c/6c mixture. To gain insight into the heme pocket structural differences between 5c and 6c Fe(ii)-NO H-NOX complexes, we investigated the extended X-ray absorption fine structure (EXAFS) of the Fe(II)-unligated and Fe(II)-NO complexes of H-NOX domains from three species, Thermoanaerobacter tengcongensis, Shewanella woodyi, and Pseudoalteromonas atlantica. Although the Fe(II)-NO complex of TtH-NOX is formally 6c, we found the Fe-N(His) bond is substantially lengthened. Furthermore, although NO binds to SwH-NOX and PaH-NOX as a 5c complex, consistent with histidine dissociation, the EXAFS data do not exclude a very weakly associated histidine. Regardless of coordination number, upon NO-binding, the Fe-N(porphyrin) bond lengths in all three H-NOXs contract by ~0.07 Å. This study reveals that the overall heme structure of 5c and 6c Fe(II)-NO H-NOX complexes are substantially similar, suggesting that formal histidine dissociation may not be required to trigger NO/H-NOX signal transduction. The study has refined our understanding of the molecular mechanisms underlying NO/H-NOX signaling.

Thermally and photo-induced spin crossover behaviour in an Fe(ii) imidazolylimine complex: [FeL3](ClO4)2

Herein we report the synthesis, structure and magnetic properties of [FeL(3)](ClO(4))(2), 1, where L is the bidentate ligand N-(4-methoxyphenyl)-1H-imidazol-2-yl-methanimine. Complex 1 crystallises as the mer-isomer which is stabilised by intramolecular π-π interactions between the methoxyphenyl 'tail' and imidazole 'head' of adjacent ligands centred around Fe(II). The crystal lattice is devoid of any significant intermolecular π-π interactions between neighbouring complexes, although hydrogen bonding between two imidazole N-H groups and two perchlorate anions links two adjacent complexes together and allows them to buttress up against one another. Structural data collected at 116 and 292 K suggest a spin-crossover (SCO) behaviour for 1 as Fe-N bond lengths increase by ca. 10% at the higher temperature. SCO behaviour is confirmed by magnetic susceptibility measurements. The χT vs. T data reveals a complete and reversible SCO for 1 with T(1/2) of 158 K, and this is further confirmed by Mössbauer spectroscopy (at 4.2 and 293 K) and variable temperature reflectivity measurements. Indeed, upon irradiation with red light (647 nm) at 10 K, 1 shows a photo-induced spin-crossover and undergoes full switching between the LS and HS states.

Tris(5-methylpyrazolyl)methane: Synthesis and Properties of Its Iron(II) Complex

The new ligand, tris(5-methylpyrazolyl)methane (1), has been prepared by the reaction of n-butyl lithium with tris(pyrazolyl)methane followed by trimethylation of the tetralithiated species with methyl iodide. The BF(4)(-), ClO(4)(-), and BPh(3)CN(-) salts of the Fe(II) complex of this ligand were also synthesized. The X-ray crystal structure of the BF(4)(-) complex (2) at 100 K had Fe-N bond lengths of 1.976 Å, indicative of a low spin Fe(II) complex, while at room temperature, the structure of this complex had a Fe-N bond distance close to 2.07 Å, indicative of an admixture of approximately 50% low-spin and 50% high-spin. The solid-state structure of the complex with a ClO(4)(-) counterion was determined at 5 different temperatures between 173 and 293 K, which allowed the thermodynamic parameters for the spin-crossover to be estimated. Mössbauer spectra of the BF(4)(-) complex further support spin-state crossover in the solid state with a transition temperature near 300 K. UV-visible spectroscopy and (1)H NMR studies of 2 show that the transition temperature in solution is closer to 400 K. No spin-crossover was observed for [Fe(1)(2)](2+)·2BPh(3)CN(-). The results allow the separation of effects of groups in the 3-position from those in the 5-position on tpm ligands, and also point toward a small cooperative effect in the spin-crossover for the Fe(II) complex.

Graphene as a Reversible Spin Manipulator of Molecular Magnets

One of the primary objectives in molecular nanospintronics is to manipulate the spin states of organic molecules with a d-electron center, by suitable external means. In this Letter, we demonstrate by first principles density functional calculations, as well as second order perturbation theory, that a strain induced change of the spin state, from S=1→S=2, takes place for an iron porphyrin (FeP) molecule deposited at a divacancy site in a graphene lattice. The process is reversible in the sense that the application of tensile or compressive strains in the graphene lattice can stabilize FeP in different spin states, each with a unique saturation moment and easy axis orientation. The effect is brought about by a change in Fe-N bond length in FeP, which influences the molecular level diagram as well as the interaction between the C atoms of the graphene layer and the molecular orbitals of FeP.

Tris(acetonitrile-κN){2,6-bis[(diphenylphosphanyl)amino]-4-ethoxy-1,3,5-triazine-κ3P,N1,P′}iron(II) bis(tetrafluoridoborate) acetonitrile disolvate

In the title compound, [Fe(CH3CN)3(C29H27N5OP2)](BF4)2·2CH3CN, the FeII ion is octa­hedrally coordinated by a meridionally chelating tridentate pincer-type PNP ligand derived from 2,6-diamino-4-eth­oxy-1,3,5-triazine and by three acetonitrile mol­ecules. The four Fe—N bond lengths range from 1.9142 (12) to 1.9579 (11) Å, while the Fe—P bonds are 2.2452 (4) and 2.2506 (4) Å [P—Fe—P = 165.523 (14)°], consistent with FeII in a low-spin state. Unlike related Fe PNP complexes based on 2,6-diamino­pyridine, the BF4 anions are not hydrogen bonded to the two NH groups of the pincer ligand but show instead anion–π inter­actions with the triazine ring and acetonitrile mol­ecules in addition to ten C—H⋯F inter­actions. Most remarkable among these is an anion–π(triazine) inter­action with a short distance of 2.788 (2) Å between one F and the centroid of the π-acidic triazine ring. The corresponding shortest distance between this F atom and a triazine carbon atom is 2.750 (2) Å. The two NH groups of the pincer ligand donate N—H⋯N hydrogen bonds to the triazine N atom of a neighbouring complex and to an uncoordinated acetonitrile mol­ecule. This last mol­ecule is in a side-on head-to-tail association with the second uncoordinated acetonitrile at C⋯N distances of 3.467 (2) and 3.569 (2) Å. In contrast to several related compounds with diamino­pyridine- instead of diamino­triazine-based PNP ligands, the title crystal structure is remarkably well ordered. This suggests that the diamino­triazine moiety exerts notable crystal structure stabilizing effects.

Acetonitriledicarbonyl(η5-pentamethylcyclopentadienyl)iron(II) tetrafluoridoborate

In the structure of the title compound, [Fe{η5-C5(CH3)5}(NCCH3)(CO)2]BF4, the arrangement of ligands around the Fe atom is in a pseudo-octa­hedral three-legged piano-stool fashion in which the penta­methyl­cyclo­penta­dienyl (Cp*) ligand occupies three apical coordination sites, while the two carbonyl and one acetonitrile ligands form the basal axes of the coordination. The Fe—N bond length is 1.924 (3) Å and the Fe—Cp* centroid distance is 1.722 Å.

Coupled Crystallographic Order–Disorder and Spin State in a Bistable Molecule: Multiple Transition Dynamics

A novel bispyrazolylpyridine ligand incorporating lateral phenol groups, H(4)L, has led to an Fe(II) spin-crossover (SCO) complex, [Fe(H(4)L)(2)][ClO(4)](2)⋅H(2)O⋅2 (CH(3))(2)CO (1), with an intricate network of intermolecular interactions. It exhibits a 40 K wide hysteresis of magnetization as a result of the spin transition (with T(0.5) of 133 and 173 K) and features an unsymmetrical and very rich structure. The latter is a consequence of the coupling between the SCO and the crystallographic transformations. The high-spin state may also be thermally trapped, exhibiting a very large T(TIESST) (≈104 K). The structure of 1 has been determined at various temperatures after submitting the crystal to different processes to recreate the key points of the hysteresis cycle and thermal trapping; 200 K, cooled to 150 K and trapped at 100 K (high spin, HS), slowly cooled to 100 K and warmed to 150 K (low spin, LS). In the HS state, the system always exhibits disorder for some components (one ClO(4)(-) and two acetone molecules) whereas the LS phases show a relative ≈9 % reduction in the Fe-N bond lengths and anisotropic contraction of the unit cell. Most importantly, in the LS state all the species are always found to be ordered. Therefore, the bistability of crystallographic order-disorder coupled to SCO is demonstrated here experimentally for the first time. The variation in the cell parameters in 1 also exhibits hysteresis. The structural and magnetic thermal variations in this compound are paralleled by changes in the heat capacity as measured by differential scanning calorimetry. Attempts to simulate the asymmetric SCO behaviour of 1 by using an Ising-like model underscore the paramount role of dynamics in the coupling between the SCO and the crystallographic transitions.

Crystal Structure of HugZ, a Novel Heme Oxygenase from Helicobacter pylori

The crystal structure of a heme oxygenase (HO) HugZ from Helicobacter pylori complexed with heme has been solved and refined at 1.8 Å resolution. HugZ is part of the iron acquisition mechanism of H. pylori, a major pathogen of human gastroenteric diseases. It is required for the adaptive colonization of H. pylori in hosts. Here, we report that HugZ is distinct from all other characterized HOs. It exists as a dimer in solution and in crystals, and the dimer adopts a split-barrel fold that is often found in FMN-binding proteins but has not been observed in hemoproteins. The heme is located at the intermonomer interface and is bound by both monomers. The heme iron is coordinated by the side chain of His(245) and an azide molecule when it is present in crystallization conditions. Experiments show that Arg(166), which is involved in azide binding, is essential for HugZ enzymatic activity, whereas His(245), surprisingly, is not, implying that HugZ has an enzymatic mechanism distinct from other HOs. The placement of the azide corroborates the observed γ-meso specificity for the heme degradation reaction, in contrast to most known HOs that have α-meso specificity. We demonstrate through sequence and structural comparisons that HugZ belongs to a new heme-binding protein family with a split-barrel fold. Members of this family are widespread in pathogenic bacteria and may play important roles in the iron acquisition of these bacteria.

Synthesis, characterization, mechanochromism and photochromism of [Fe(dm4bt)3][FeCl4]2 and [Fe(dm4bt)3][FeBr4]2, along with the investigation of steric influence on spin state

The complexes [Fe(dm4bt)(3)][FeCl(4)](2) (1) and [Fe(dm4bt)(3)][FeBr(4)](2) (2) were prepared from the reaction of 2,2'-dimethyl-4,4'-bithiazole (dm4bt) with FeCl(3)·6H(2)O and FeBr(3), respectively, in methanol. Both complexes were characterized by IR, UV-Vis and (1)H NMR spectroscopy and their structures were studied by single-crystal diffraction. The methylated bithiazole led to high spin Fe(II) centers in the octahedral cation part of complexes 1 and 2 with Fe-N distance of 2.220 Å, in spite of the low spin octahedral Fe(II) complexes with unsubstituted bithiazole ligands. Crystal structure determination of 2 was performed at 90, 120 and 298 K. Temperature reduction to 90 K resulted in a decrease in the Fe-N bond length to 2.206 Å which is still in the range of high spin Fe(II). Complex 1 shows a reversible mechanochromic effect from the crystalline phase to powder form from red to yellow; it also displays reversible photochromism from yellow to green in solution under sunlight. The magnetic behaviour of the complexes was also studied at 2-300 K. The temperature dependence of χ(m)T curves for the two forms of 1, crystal and powder, demands some changes in their magnetic behavior, causing different colors i.e. red and yellow. At low temperatures, χ(m)T decreases where the decrease starts at around 65 K for compound 1, and at around 100 K for compound 2, due to different counterions. The two complexes exhibit antiferromagnetism at around 4 K.

Photo-Induced Spin-State Conversion in Solvated Transition Metal Complexes Probed via Time-Resolved Soft X-ray Spectroscopy

Solution-phase photoinduced low-spin to high-spin conversion in the Fe(II) polypyridyl complex [Fe(tren(py)(3))](2+) (where tren(py)(3) is tris(2-pyridylmethyliminoethyl)amine) has been studied via picosecond soft X-ray spectroscopy. Following (1)A(1) --> (1)MLCT (metal-to-ligand charge transfer) excitation at 560 nm, changes in the iron L(2)- and L(3)-edges were observed concomitant with formation of the transient high-spin (5)T(2) state. Charge-transfer multiplet calculations coupled with data acquired on low-spin and high-spin model complexes revealed a reduction in ligand field splitting of approximately 1 eV in the high-spin state relative to the singlet ground state. A significant reduction in orbital overlap between the central Fe-3d and the ligand N-2p orbitals was directly observed, consistent with the expected ca. 0.2 A increase in Fe-N bond length upon formation of the high-spin state. The overall occupancy of the Fe-3d orbitals remains constant upon spin crossover, suggesting that the reduction in sigma-donation is compensated by significant attenuation of pi-back-bonding in the metal-ligand interactions. These results demonstrate the feasibility and unique potential of time-resolved soft X-ray absorption spectroscopy to study ultrafast reactions in the liquid phase by directly probing the valence orbitals of first-row metals as well as lighter elements during the course of photochemical transformations.

Redox Effects on the Coordination Geometry and Heme Conformation of Bis(N-methylimidazole) Complexes of Superstructured Fe-Porphyrins. A Spectroscopic Study

Electronic absorption, electron paramagnetic resonance (EPR), and Soret-excited resonance Raman (RR) spectra are reported for bis(N-alkylimidazole) complexes of various iron(III)-"basket-handle" (Fe(III)BHP(+)) and "picket-fence" (Fe(III)PFP(+)) porphyrins in methylene chloride. The Fe(III)BHP(+) derivatives consist of four cross-trans (CT) and two adjacent-cis (AC) -linked in which the composition and the length of the handles are variable (CT Fe(III)[(C(11)Im)(2)(+)], CT and AC Fe(III)[((C(4))(2)phi)(2)](+), CT Fe(III)[((C(3))(2)phi)(C(12))](+), CT and AC Fe(III)[((C(3))(2)phi)(2)](+)). The meso-alphaalpha betabeta and meso-alphabeta alphabeta atropisomers of Fe(III)-tetrakis(o-pivalamidophenyl)-porphyrins represents the Fe(III)PFP(+) derivatives (Fe(III)alphaalpha betabeta-T(piv)PP(+) and Fe(III)alphabeta alphabeta-T(piv)PP(+), respectively). The absorption and RR data obtained for these ferric compounds were compared to those previously published for the homologous ferrous complexes (Picaud, T., Le Moigne, C., Loock, B., Momenteau, M. and Desbois, A. J. Am. Chem. Soc. 2003, 125, 11616 and Le Moigne, C., Picaud, T., Boussac, A., Loock, B., Momenteau, M. and Desbois, A. Inorg. Chem. 2003, 42, 6081). The Soret band position of the eight investigated ferric compounds is observed between 417 and 424 nm, indicating that none of the complexes possesses a planar heme. The EPR spectra show that most of the Fe(III)BHP(+) complexes and all the Fe(III)PFP(+) complexes are rhombic B-type hemichromes (g(max) = 2.86-2.96). Notable exceptions concern the bis(N-methylimidazole) complexes of two CT Fe(III)BHP(+). The Fe(III)BHP(+) with the shortest handles (Fe(III)[((C(3))(2)phi)(2)](+)) exhibits a g value at 2.80. When the handles are lengthened by two methylene units (Fe(III)[((C(3))(2)phi)(2)](+)), the EPR spectrum corresponds to a mixture of two "highly anisotropic low-spin " or "large g(max)" type I EPR signals, a major species at g = 3.17 and a minor species at g = 3.77. All these EPR data were converted in terms of dihedral angle formed by the rings of the axial ligands. The RR spectra of the Fe(III)BHP(+) and Fe(III)PFP(+) complexes exhibited variable frequencies for the structure-sensitive nu(2) and nu(8) lines (1558-1563 cm(-1) and 386-401 cm(-1), respectively). In considering the ability of the different superstructures to stabilize particular out-of-plane distortions, this vibrational information was analyzed in terms of heme structure through changes in core size and Fe-N(pyrrole) bond length, in relation to changes in coordination geometry. The bis(N-methylimidazole) complex of Fe(III)[((C(3))(2)phi)(2)](+) was found to be the most distorted with a strongly ruffled tetrapyrrole. Because of a handle asymmetry, the heme conformation of the bis(N-methylimidazole) complex of Fe(III)[((C(3))(2)phi)(C(12))](+) was deduced to be a composition of ruffled and domed structures. The heme structure of the other complexes is a mixture of ruffled and saddled or ruffled and waved conformations. Taking into account our previous data on the ferrous series, this investigation provides information about the reorganization of the heme structure upon iron oxidation. The general trend is a decrease of either the core-size, or the Fe-N(pyrrole) bond length, or both. However, we demonstrated that the heme superstructures precisely control the nature and the extent of the tetrapyrrole reshaping. These results point out similar possible effect in the heme proteins, considering both an analogy between porphyrin superstructures and amino acids forming the heme sites and the diversity of the heme environments in the proteins.

Ligand Strain and the Nature of Spin Crossover in Binuclear Complexes: Two‐Step Spin Crossover in a 4,4′‐Bipyridine‐Bridged Iron(II) Complex [{Fe(dpia)(NCS)2}2(4,4′‐bpy)] (dpia=di(2‐picolyl)amine; 4,4′‐bpy=4,4′‐bipyridine)

The synthesis and detailed characterization of the new spin crossover (SCO) binuclear complex [{Fe(dpia)(NCS)(2)}(2)(4,4'-bpy)] (1; dpia=di(2-picolyl)amine, 4,4'-bpy = 4,4'-bipyridine) are reported. Variable-temperature magnetic susceptibility measurements show a relatively cooperative two-step spin transition suggesting the occurrence of three spin-state isomers: [HS-HS], [HS-LS], and [LS-LS] (HS: high spin, LS: low spin). A short plateau at 204 K separates the two steps and conforms with about 50% of the complexes having undergone a thermal spin conversion. Routine Mössbauer spectroscopy without applying a magnetic field clearly separates four iron(II) one-center spin states in three [HS-HS], [HS-LS], and [LS-LS] pairs and unambiguously confirms that the spin transition at the plateau temperature goes through the intermediate [HS-LS] state. The single-crystal X-ray structure was solved for three spin isomers at 293, 208, and 120 K. The structural study at the plateau temperature was unable to resolve the HS and LS sites in the [HS-LS] pair and only an average Fe-N bond length was obtained, which suggests that there is an intermediate [HS-LS] phase. The structural analysis at three temperatures revealed a dense three-dimensional network of both intra- and intermolecular interactions. The relative energies of the three spin-state isomers were evaluated by quantum-chemical DFT calculations. Comparison of compound 1 with previously known analogues, as well as the overall analysis of structural data for numerous binuclear complexes, allowed a conclusion to be reached on the crucial role of ligand strain effects in the SCO behavior of binuclear complexes. The suggested intramolecular mechanism explains the different types of SCO observed in binuclear complexes: one-step, two-step, and partial (50%) transitions.