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Philipp Gütlich

Publications and source records attributed to Philipp Gütlich.

At least 19 recordsLinked to original sources
PubMed2006

Mössbauer investigation of the photoexcited spin states and crystal structure analysis of the spin-crossover dinuclear complex [{Fe(bt)(NCS)(2)}(2)bpym] (bt=2,2'-bithiazoline, bpym=2,2'-bipyrimidine).

The crystal structure of the complex [{Fe(bt)(NCS)(2)}(2)bpym] (1) (bt=2,2'-bithiazoline, bpym=2,2'-bipyrimidine) has been solved at 293, 240, 175 and 30 K. At all four temperatures the crystal remains in the P space group with a=8.7601(17), b=9.450(2), c=12.089(3) A, alpha=72.77(2), beta=79.150(19), gamma=66.392(18) degrees , V=873.1(4) Angstrom(3) (data for 293 K structure). The structure consists of centrosymmetric dinuclear units in which each iron(II) atom is coordinated by two NCS(-) ions in the cis position and two nitrogen atoms of the bridging bpym ligand, with the remaining positions occupied by the peripheral bt ligand. The iron atom is in a severely distorted octahedral FeN(6) environment. The average Fe--N bond length of 2.15(9) Angstrom indicates that compound 1 is in the high-spin state (HS-HS) at 293 K. Crystal structure determinations at 240, 175 and 30 K gave a cell comparable to that seen at 293 K, but reduced in volume. At 30 K, the average Fe--N distance is 1.958(4) Angstrom, showing that the structure is clearly low spin (LS-LS). At 175 K the average Fe--N bond length of 2.052(11) Angstrom suggests that there is an intermediate phase. Mössbauer investigations of the light-induced excited spin state trapping (LIESST) effect (lambda=514 nm, 25 mW cm(-2)) in 1 (4.2 K, H(ext)=50 kOe) show that the excited spin states correspond to the HS-HS and HS-LS pairs. The dynamics of the relaxation of the photoexcited states studied at 4.2 K and H(ext)=50 kOe demonstrate that HS-HS pairs revert with time to both HS-LS and LS-LS configurations. The HS-LS photoexcited pairs relax with time back to the ground LS-LS configuration. Complex [{Fe(0.15)Zn(0.85)(bt)(NCS)(2)}(2)bpym] (2) exhibits a continuous spin transition centred around 158 K in contrast to the two-step transition observed for 1. The different spin-crossover behaviour observed for 2 is due to the decrease of cooperativity (intermolecular interactions) imposed by the matrix of Zn(II) ions. This clearly demonstrates the role of the intermolecular interactions in the stabilization of the HS-LS intermediate state in 1.

Journal Article↗
PubMed2006

Vibrational spectrum of the spin crossover complex [Fe(phen)(2)(NCS)(2)] studied by IR and Raman spectroscopy, nuclear inelastic scattering and DFT calculations.

The vibrational modes of the low-spin and high-spin isomers of the spin crossover complex [Fe(phen)(2)(NCS)(2)] (phen = 1,10-phenanthroline) have been measured by IR and Raman spectroscopy and by nuclear inelastic scattering. The vibrational frequencies and normal modes and the IR and Raman intensities have been calculated by density functional methods. The vibrational entropy difference between the two isomers, DeltaS(vib), which is--together with the electronic entropy difference DeltaS(el)--the driving force for the spin-transition, has been determined from the measured and from the calculated frequencies. The calculated difference (DeltaS(vib) = 57-70 J mol(-1) K(-1), depending on the method) is in qualitative agreement with experimental values (20-36 J mol(-1) K(-1)). Only the low energy vibrational modes (20% of the 147 modes of the free molecule) contribute to the entropy difference and about three quarters of the vibrational entropy difference are due to the 15 modes of the central FeN(6) octahedron.

Ferrous Compounds↗
PubMed2006

Decacyclene as complexation manifold: synthesis, structure and properties of its Fe2 and Fe4 slipped triple-decker complexes.

Reaction of [(eta(5)-Me4EtC5)Fe(II)Cl(tmeda)] (tmeda = N,N,N'N'-tetramethylethylenediamine) with a polyanion solution of decacyclene (1) results in the formation of the triple-deckers [{(eta(5)-Me4EtC5)Fe}2-mu2-(eta(6):eta(6)-decacyclene)] (3) and [{(eta(5)-Me4EtC5)Fe}4-mu4-(eta(6):eta(6):eta(6):eta(6)-decacyclene)] (4). Metal complexation in 3 and 4 occurs on opposite faces of the pi perimeter in an alternating mode. The decacyclene ring adopts a gently twisted molecular propeller geometry with twofold crystallographic symmetry (C2). Complex 4 crystallizes in the chiral space group C222(1); the investigated crystal only contains decacyclene rings with M chirality. The handedness can be assigned unambiguously to the presence of the iron atoms. Cyclovoltammetric studies revealed quasireversible behavior of the redox events and a strong interaction of the Fe atoms in 3 and 4, exemplified by potential differences deltaE of 660 and 770(780) mV between the first and the second individual oxidation processes. This corresponds to a high degree of metal-metal interaction for 3 and 4. The successful syntheses of 3 and 4 together with earlier results from our laboratory proves that all five- and six-membered pi subunit sets of 1 are prone to metal complexation. A clear site preference in 1 towards the complexation of [Cp(R)]iron, -cobalt, and -nickel fragments exists.

Journal Article↗
PubMed2005

Crystal structure, magnetic properties, and 57Fe Mössbauer spectroscopy of the two-dimensional coordination polymers [M(1,2-bis(1,2,4-triazol-4-yl)ethane)2(NCS)2] (MII = Fe, Co).

New coordination polymers of the formula [M(btre)(2)(NCS)(2)] (btre = 1,2-bis(1,2,4-triazol-4-yl)ethane; M(II) = Fe, Co) have been synthesized, and their crystal structures have been determined at 293 K by X-ray analysis. The Fe(II) compound (C(7)H(8)FeN(7)S(2)) crystallizes in the monoclinic space group P2(1)/n, a = 12.439(5) A, b = 8.941(2) A, c = 9.321(3) A, beta = 90.88(2) degrees , V = 1036.6(6) A(3), Z = 2, 3791 reflections [I > 3sigma(I)], R(F) = 0.036, wR2 = 0.123. The Co(II) compound is isostructural to the Fe(II) compound. The crystal structure consists of a 2D sheet in which the metal ions are linked by bis monodentate (N1, N1') 1,2,4-triazole ligands. The structure is stabilized by pi-bond interactions between two adjacent sheets and by S...S interactions. Temperature-dependent SQUID, (57)Fe Mössbauer, and X-ray diffraction measurements indicate that [Fe(btre)(2)(NCS)(2)] retains a HS ground state upon cooling from 293 K down to 8 K. The surprising absence of spin-crossover behavior for this Fe(II)-1,2,4-triazole polymeric coordination compound that has been confirmed by pressure experiments up to approximately 12 kbar and by light irradiation experiments at 10 K is discussed on the basis of its structural features. Insight into the origin of the cooperative effects of the spin transition in [Fe(btr)(2)(NCS)(2)].H(2)O (btr = 4,4'-bis-1,2,4-triazole) is also given thanks to a re-evaluation of its distortion parameters in the high- and low-spin states.

Journal Article↗
PubMed2005

Electronic, vibrational, and structural properties of a spin-crossover catecholato-iron system in the solid state: theoretical study of the electronic nature of the doublet and sextet states.

As a functional model of the catechol dioxygenases, [(TPA)Fe(Cat)]BPh4 (TPA = tris(2-pyridylmethyl)amine and Cat = catecholate dianion) exhibits the purple-blue coloration indicative of some charge transfer within the ground state. In contrast to a number of high-spin bioinspired systems, it was previously shown that, in the solid state, [(TPA)Fe(Cat)]BPh4 undergoes a two-step S = 1/2 = S = 5/2 spin-crossover. Therefore, the electronic and vibrational characteristics of this compound were investigated in the solid state by UV/Vis absorption and resonance Raman spectroscopies over the temperature range of the transition. This allowed the charge-transfer transitions of the low-spin (LS) form to be identified. In addition, the vibrational progression observed in the NIR absorption of the LS form was assigned to a five-membered chelate ring mode. The X-ray crystal structure solved at two different temperatures, shows the presence of highly distorted pseudo-octahedral ferric complexes that occupy two nonequivalent crystalline sites. The variation of the molecular parameters as a function of temperature strongly suggests that the two-step transition proceeds by a successive transition of the species in the two nonequivalent sites. The thermal dependence of the high-spin fraction of metal ions determined by Mössbauer experiments is consistent with the magnetic data, except for slight deviations in the high temperature range. The optimized geometries, the electronic transitions, vibrational frequencies, and thermodynamic functions were calculated with the B3LYP density functional method for the doublet and the sextet states. The finding of a ground state that possesses a significant mixture of Fe(III)-catecholate and FeII-semiquinonate configurations is discussed with regard to the set of experimental and theoretical data.

Journal Article↗
PubMed2004

Hierarchical self-assembly of supramolecular spintronic modules into 1D- and 2D-architectures with emergence of magnetic properties.

Hierarchical self-assembly of complex supramolecular architectures allows for the emergence of novel properties at each level of complexity. The reaction of the ligand components A and B with Fe(II) cations generates the [2x2] grid-type functional building modules 1 and 2, presenting spin-transition properties and preorganizing an array of coordination sites that sets the stage for a second assembly step. Indeed, binding of La(III) ions to 1 and of Ag(I) ions to 2 leads to a 1D columnar superstructure 3 and to a wall-like 2D layer 4, respectively, with concomitant modulation of the magnetic properties of 1 and 2. Thus, to each of the two levels of structural complexity generated by the two sequential self-assembly steps corresponds the emergence of novel functional features.

Journal Article↗
PubMed2004

On the nature of the plateau in two-step dinuclear spin-crossover complexes.

A remarkable feature of the spin-crossover process in several dinuclear iron(II) compounds is a plateau in the two-step transition curve. Up to now, it has not been possible to analyse the spin state of dinuclear pairs that constitute such a plateau, due to the relative high temperatures at which the transition takes place in complexes investigated so far. We solved this problem by experimentally studying a novel dinuclear spin-crossover compound [[Fe(phdia)(NCS)(2)](2)(phdia)] (phdia: 4,7-phenanthroline-5,6-diamine). We report here on the synthesis and characterisation of this system, which exhibits a two-step spin transition at T(c1)=108 K and T(c2)=80 K, displaying 2 K and 7 K wide thermal hysteresis loops in the upper and the lower steps, respectively. A plateau of approximately 20 K width centred at about 90 K, which corresponds to the 50 % of the spin conversion, separates the two transitions. The composition of the plateau was identified in metastable state after quenching to 4.2 K by means of Mössbauer spectroscopy in an external magnetic field. Such experiments revealed that the plateau consists mainly of [HS-LS] pairs (HS=high spin, LS=low spin) and confirmed the hypothesis that the spin conversion in dinuclear entities proceeds through [LS-LS]<-->[HS-LS]<-->[HS-HS] pairs. The results are discussed in terms of a thermodynamic model based on the regular solution theory adapted for dinuclear spin-crossover compounds.

Journal Article↗
PubMed2004

An inorganic double helix sheathing alkali metal cations: ANb2P2S12 (A=K, Rb, Cs), a series of thiophosphates close to the metal-nonmetal boundary--chalcogenide analogues of transition-metal phosphate bronzes?

The new quaternary niobium thiophosphates ANb(2)P(2)S(12) (A=K, Rb, Cs) have been prepared and characterized. The title compounds were synthesized by reacting Nb metal, A(2)S, P(2)S(5), and S at 600-700 degrees C in evacuated silica tubes. They crystallize as "stuffed" variants of the tetragonal TaPS(6) structure type in the tetragonal space group I$\bar 4$2d with eight formula units per unit cell and lattice constants a=15.923(2) and c=13.238(3) A for CsNb(2)P(2)S(12), a=15.887(3) and c=13.132(3) A for RbNb(2)P(2)S(12), and a=15.850(2) and c=13.119(3) A for KNb(2)P(2)S(12). Their structures are based on double helices formed from interpenetrating, noninteracting spiral chains of binuclear [Nb(2)S(12)] cluster units and [PS(4)] thiophosphate groups. The cavities and tunnels, which are formed by the helical chains, are filled with A(+) ions. Temperature-dependent conductivity studies reveal thermally activated electrical transport behavior. This result is consistent with the observation of a temperature-dependent contribution to the (31)P MAS-NMR shift, suggesting that the delocalized s-electron spin density increases with increasing temperature. These findings are supported by the results of tight-binding band structure calculations which reveal that the unusual electrical transport behavior of ANb(2)P(2)S(12) is a consequence of the structure symmetry. Therefore, CsNb(2)P(2)S(12) may be considered a chalcogenide analogue of metal phosphate bronzes.

Journal Article↗
PubMed2002

A spin transition molecular material with a wide bistability domain.

[Fe(hyptrz)3](4-chloro-3-nitrophenylsulfonate)22 H2O (1; hyptrz=4-(3-hydroxypropyl)-1,2,4-triazole) has been synthesized and its physical properties have been investigated by several physical techniques including magnetic susceptibility measurements, calorimetry, and Mössbauer, optical, and EXAFS spectroscopy. Compound 1 exhibits a spin transition below room temperature, together with a very wide thermal hysteresis of about 50 K. This represents the widest hysteresis loop ever observed for an FeII-1,2,4-triazole spin transition material. The cooperativity is discussed on the basis of temperature-dependent EXAFS studies and of the structural features of a CuII analogue. The EXAFS structural model of (1) in both spin states is compared to that obtained for a related material whose spin transition occurs above room temperature. EXAFS spectroscopy suggests that 1,2,4-triazole chain compounds retain a linear character whatever the spin state of the iron(II).

Journal Article↗
PubMed1999

An Iron-Based Molecular Redox Switch as a Model for Iron Release from Enterobactin via the Salicylate Binding Mode.

The iron release mechanism from protonated ferric enterobactin [Fe(III)(enterobactinH(3))] via the salicylate binding mode was probed. For this purpose, a tripodal dodecadentate ligand incorporating three salicylamide (OO) and three bipyridine (NN) binding sites was synthesized as well as iron complexes thereof. It was shown that a ferric ion coordinates selectively to the hard salicylamides and a ferrous ion binds to the softer bipyridines. Upon reduction or oxidation, the iron translocates reversibly and intramolecularly from one site to the other, thus displaying switchlike properties. Both states were characterized by cyclic voltammetry and visible and Mössbauer spectroscopy. The Mössbauer spectrum for the ferric complex is fully consistent with that obtained by Pecoraro et al. upon lowering the pH of [Fe(III)(enterobactin)](3)(-) solutions (Pecoraro, V. L., et al. J. Am. Chem. Soc. 1983, 105, 4617), thus supporting the alternative iron release mechanism from enterobactin via the salicylate binding mode.

Journal Article↗
PubMed1999

Bis-macrocyclic Ligands with Two Ferrocenyl End Groups, and Their Tetranuclear Dicopper(I) Compounds.

A series of bismacrocyclic ligands with two ferrocenyl groups, exo/endo-1,1':1' ',1' "-[1,2,4,5-tetrakis(5-aza-2-thiahexa-5-enyl)benzene]bisferrocene (exo/endo-FeBeFe), 1,1':1' ',1' "-[1,2:1',2'-tetrakis(5-aza-2-thiahexa-5-enyl)ethene]bisferrocene (1,2-FeEnFe), 1,1':1' ',1' "-[1,1':2,2'-tetrakis(5-aza-2-thiahexa-5-enyl)ethene]bisferrocene (1,1-FeEnFe), 1,1':1' ',1' "-[tetrakis(5-aza-2-thiahexa-5-enyl)methane]bisferrocene (FeMeFe), and their dicopper(I) compounds have been synthesized and characterized (electrochemistry, IR, NMR and Mössbauer spectroscopy). The molecular structure of endo-FeBeFe has been determined by X-ray structure analysis and the copper(I)-induced discrimination of the exo- and endo-isomers of FeBeFe has been investigated by (1)H NMR spectroscopy. The interaction between copper and iron in the tetranuclear compounds is discussed on the basis of the electrochemical and spectroscopic data.

Journal Article↗
PubMed1997

Electron Transfer in Mixed-Valence [Fe(III)(2)Fe(II)O(O(2)CCH(3))(6)(3-Cl-py)(3)].3-Cl-py: Effects of a Crystallographic Phase Transition and Conversion of Solvate and Ligand Molecules from Statically Disordered to Dynamically Disordered on the Valence Detrapping.

A crystallographic phase transition involving changes in the solvate molecule has been found for mixed-valence [Fe(3)O(O(2)CCH(3))(6)(3-Cl-py)(3)].3-Cl-py (1), where 3-Cl-py is 3-chloropyridine. Single-crystal X-ray structures were determined at 300, 228, 200, 169, and 122 K for complex 1. At 300, 228, and 200 K the crystal is monoclinic, space group P2(1)/c, whereas at 169 and 122 K it is triclinic, space group P&onemacr;. Determinations of the unit cell parameters at several temperatures shows that a reversible crystallographic phase transition between the monoclinic and triclinic forms occurs at approximately 200 K. Complex 1 crystallizes in the monoclinic space group P2(1)/c at 300 K, having a unit cell with a = 21.212(8) Å, b = 8.434(2) Å, c = 23.676(3) Å, and Z = 4. Refinement with 5702 observed [F(o) > 4sigma(F(o))] reflections gave R = 0.0542 and R(w) = 0.0937. Complex 1 crystallizes in the triclinic space group P&onemacr; at 122 K, having a unit cell with a = 20.983(11) Å, b = 8.360(4) Å, c = 23.293(10) Å, and Z = 4. At 300 K there is one somewhat asymmetric Fe(3)O complex in the structure. The core dimensions in the Fe(3)O complex at 300 K indicate that the complex is becoming almost valence-detrapped. At 122 K there are two different Fe(3)O complexes in the unit cell, both of which are similar in dimensions. As the temperature is decreased from 300 to 122 K, each Fe(3)O complex becomes more and more distorted in an equilateral triangle. At 122 K one iron ion in each Fe(3)O complex clearly is a high-spin Fe(II) ion and the other two are high-spin Fe(III) ions. There are significant changes in the nature of the 3-Cl-py solvate molecules above and below the phase transition that are likely important in controlling the valence detrapping. At 122 K there are two different Fe(3)O complexes, each with their nearby 3-Cl-py solvate molecules in one position. There are three different phases: a monoclinic one with all solvate molecules disordered, a second triclinic phase at 169 K with half of the solvate molecules disordered, and a third triclinic phase at 122 K with all solvate molecules statically ordered. (57)Fe Mössbauer spectra taken in the 110-293 K range show that complex 1 converts from valence-trapped at 110 K to become detrapped by 293 K, where a single quadrupole-split doublet is seen. Throughout the 140-230 K range it was necessary to employ one Fe(III) doublet and two Fe(II) doublets to fit each Mössbauer spectrum. It is shown that the two Fe(II) doublets likely arise from Fe(3)O complexes experiencing the different disordered solvate environments described above. Thus, while the approximately 200 K structural phase transition involving the solvate molecules does not precipitously lead to an increase in the rate of electron transfer in Fe(3)O complexes in 1, it is clear that the changes seen in the solvate molecules from X-ray structures do play a major role in the valence detrapping in complex 1.

Journal Article↗
PubMed1997

Synthesis, Structure, Magnetic Behavior, and Mössbauer Spectroscopy of Two New Iron(II) Spin-Transition Compounds with the Ligand 4-Isopropyl-1,2,4-triazole. X-ray Structure of [Fe(3)(4-isopropyl-1,2,4-triazole)(6)(H(2)O)(6)](tosylate)(6).2H(2)O.

Two new iron(II) compounds with the formula [Fe(3)(iptrz)(6)(H(2)O)(6)]X(6).xH(2)O (with iptrz = 4-isopropyl-1,2,4-triazole and X = p-toluenesulfonate (Tos) or trifluoromethanesulfonate (Trifl)) were synthesized. The crystal structure of [Fe(3)(iptrz)(6)(H(2)O)(6)](Tos)(6).2H(2)O (I) has been solved at room temperature. Crystals of I are triclinic, space group P&onemacr; with a = 12.8820(11) Å, b = 15.580(2) Å, c = 24.445(4) Å, alpha = 79.270(12) degrees, beta = 86.688(11) degrees, gamma = 83.007(8) degrees, Z = 2. The structure of I consists of linear trinuclear cations with a +6 charge and noncoordinated anions and lattice water molecules. The central iron ion is located on an inversion center and is coordinated by 6 nitrogen atoms of 6 iptrz molecules bridging via the nitrogen atoms in the 1,2-positions. Each external iron atom completes its coordination sphere with three coordinated water molecules. The temperature dependent magnetic measurements of compound I and [Fe(3)(iptrz)(6)(H(2)O)(6)](Trifl)(6) (II) show that both compounds exhibit a gradual spin conversion of the central iron ion centered at T(1/2) = 242 K for I and 187 K for II. Temperature dependent Mössbauer spectroscopy measurements on I show the behavior expected for a compound of this nature. The measurements on II indicate a strong influence of the spin conversion of the central iron ion on both external iron ions. The nature of this phenomenon is proposed to be connected to a very rigid lattice structure (ionic, H-bonding) connecting the trinuclear units.

Journal Article↗