High-spin Ions Research Articles

Quantum Magnetism of the Iron Core in Ferritin Proteins-A Re-Evaluation of the Giant-Spin Model.

The electron-electron, or zero-field interaction (ZFI) in the electron paramagnetic resonance (EPR) of high-spin transition ions in metalloproteins and coordination complexes, is commonly described by a simple spin Hamiltonian that is second-order in the spin S: H=D[Sz2-SS+1/3+E(Sx2-Sy2). Symmetry considerations, however, allow for fourth-order terms when S ≥ 2. In metalloprotein EPR studies, these terms have rarely been explored. Metal ions can cluster via non-metal bridges, as, for example, in iron-sulfur clusters, in which exchange interaction can result in higher system spin, and this would allow for sixth- and higher-order ZFI terms. For metalloproteins, these have thus far been completely ignored. Single-molecule magnets (SMMs) are multi-metal ion high spin complexes, in which the ZFI usually has a negative sign, thus affording a ground state level pair with maximal spin quantum number mS = ±S, giving rise to unusual magnetic properties at low temperatures. The description of EPR from SMMs is commonly cast in terms of the 'giant-spin model', which assumes a magnetically isolated system spin, and in which fourth-order, and recently, even sixth-order ZFI terms have been found to be required. A special version of the giant-spin model, adopted for scaling-up to system spins of order S ≈ 103-104, has been applied to the ubiquitous iron-storage protein ferritin, which has an internal core containing Fe3+ ions whose individual high spins couple in a way to create a superparamagnet at ambient temperature with very high system spin reminiscent to that of ferromagnetic nanoparticles. This scaled giant-spin model is critically evaluated; limitations and future possibilities are explicitly formulated.

Modeling of the Charge-Transfer-Induced Spin Transition in the Tetranuclear Cyanide-Bridged [Co2Fe2] Complex.

The course of the charge-transfer-induced spin transition demonstrated by the cyanide-bridged tetranuclear [Co2Fe2(bpy*)4(CN)6(tp*)2](PF6)2·2CP·8BN complex has been followed by DFT calculations of the single-point energies for different total spin values of the complex in a wide temperature range. With the aid of these calculations, the picture of spin conversion, that the compound undergoes, has been restored. It has been demonstrated that at 100 K the two crystallographically unique tetranuclear Fe2Co2 subunits A and B present in the structure contain diamagnetic low-spin FeII and low-spin CoIII ions. From the three subunits A, A', and B detected crystallographically in the compound at 200 K, only the A ones contain paramagnetic low-spin FeIII and high-spin CoII ions, while at 260 K, a half of all clusters contained in the crystal are in this state. From the DFT calculations, it also follows that at 320 K in the crystal only paramagnetic units are present. The results obtained are in accordance with the experimental data on the magnetic susceptibility. A possibility to predict new materials exhibiting spin transitions on the basis of DFT calculations of single-point energies as functions of temperature is discussed.

Manganese(ii) complexes of hexaazatrinaphthylene and hexaazatrianthracene: synthesis, structure and properties

A series of complexes containing dianionic and radical-trianionic hexaazatriphenylene (HATNA) and hexazatrianthracene (HATA) ligands and high-spin MnII ions (S = 5/2) were obtained. It is shown that elongation of the Mn–N bonds results in a decrease of both Mn–ligand and Mn–Mn couplings.

FeIII in the high-spin state in dimethylammonium bis[3-ethoxysalicylaldehyde thiosemicarbazonato(2-)-κ3O2,N1,S]ferrate(III).

The synthesis and crystal structure (100 K) of the title compound, [(CH3)2NH2][Fe(C10H11O2N3S)2], are reported. The asymmetric unit consists of an octahedral [FeIII(L)2]- fragment, where L2- is 3-ethoxysalicylaldehyde thiosemicarbazonate(2-), and a dimethylammonium cation. Each L2- ligand binds with the thiolate S, the imine N and the phenolate O atoms as donors, resulting in an FeIIIS2N2O2 chromophore. The ligands are orientated in two perpendicular planes, with the O and S atoms in cis positions, and mutually trans N atoms. The FeIII ion is in the high-spin state at 100 K. The variable-temperature magnetic susceptibility measurements (5-320 K) are consistent with the presence of a high-spin FeIII ion with D= 0.83 (1) cm-1 and g= 2.

New HATNA(CN)6 ligand in the design of dianion magnetic assemblies with lanthanides {Cryptand(K+)}2{HATNA(CN)6·3LnIII(TMHD)3}2− (Ln = Gd, Tb and Dy)

Hexaazatrinaphthylenehexacarbonitrile ligand, HATNA(CN)6, when reduced to dianion state, forms crystalline {Cryptand[2.2.2](K+)}2{HATNA(CN)6}2−·2C6H4Cl2 (1) salt whose structure, optical and magnetic properties are studied. The HATNA(CN)6}2− dianions absorb light in the whole visible and a wide NIR range from 900 up to 2200 nm and have singlet EPR silent ground state. The dianions form trinuclear {Cryptand[2.2.2](K+)}2{HATNA(CN)6·3LnIII(TMHD)3}2−·3C6H5CH3 complexes where Ln is Gd (2), Tb (3) and Dy (4), and TMHD is 2,2,6,6-tetramethyl-3,5-heptanedionate. The {HATNA(CN)6}2− dianions are strongly distorted in coordination assemblies and have the length of the La-N{HATNA(CN)6} bonds of 2.58–2.66 Å. Dianions preserve low-energy absorption at the coordination of three metal complexes with maxima of the bands at 1440–1460 nm. DFT calculations support strong acceptor properties of HATNA(CN)6 and the non-degenerated LUMO for this ligand. As a result, dianions have singlet ground state whereas triplet state is positioned higher by 139 meV only (1620 K) and is thermally unattainable at 300 K. Coordination of the lanthanide complexes increases the singlet–triplet gap up to 210 meV (2440 K). Complexes 2–4 show weak antiferromagnetic coupling between high-spin lanthanide ions. J value estimated by PHI program for the gadolinium-complex is close to zero. Among 2–4 only gadolinium-containing complex 2 manifests an EPR signal with a complicated structure which can be approximated with D = 0.19 and E = 0.02 cm−1.

Tale of Three Molecular Nitrides: Mononuclear Vanadium (V) and (IV) Nitrides As Well As a Mixed-Valence Trivanadium Nitride Having a V3N4 Double-Diamond Core.

Transmetallation of [VCl3(THF)3] and [TlTptBu,Me] afforded [(TptBu,Me)VCl2] (1, TptBu,Me = hydro-tris(3-tert-butyl-5-methylpyrazol-1-yl)borate), which was reduced with KC8 to form a C3v symmetric VII complex, [(TptBu,Me)VCl] (2). Complex 1 has a high-spin (S = 1) ground state and displays rhombic high-frequency and -field electron paramagnetic resonance (HFEPR) spectra, while complex 2 has an S = 3/2 4A2 ground state observable by conventional EPR spectroscopy. Complex 1 reacts with NaN3 to form the VV nitride-azide complex [(TptBu,Me)V≡N(N3)] (3). A likely VIII azide intermediate en route to 3, [(TptBu,Me)VCl(N3)] (4), was isolated by reacting 1 with N3SiMe3. Complex 4 is thermally stable but reacts with NaN3 to form 3, implying a bis-azide intermediate, [(TptBu,Me)V(N3)2] (A), leading to 3. Reduction of 3 with KC8 furnishes a trinuclear and mixed-valent nitride, [{(TptBu,Me)V}2(μ4-VN4)] (5), conforming to a Robin-Day class I description. Complex 5 features a central vanadium ion supported only by bridging nitride ligands. Contrary to 1, complex 2 reacts with NaN3 to produce an azide-bridged dimer, [{(TptBu,Me)V}2(1,3-μ2-N3)2] (6), with two antiferromagnetically coupled high-spin VII ions. Complex 5 could be independently produced along with [(κ2-TptBu,Me)2V] upon photolysis of 6 in arene solvents. The putative {VIV≡N} intermediate, [(TptBu,Me)V≡N] (B), was intercepted by photolyzing 6 in a coordinating solvent, such as tetrahydrofuran (THF), yielding [(TptBu,Me)V≡N(THF)] (B-THF). In arene solvents, B-THF expels THF to afford 5 and [(κ2-TptBu,Me)2V]. A more stable adduct (B-OPPh3) was prepared by reacting B-THF with OPPh3. These adducts of B are the first neutral and mononuclear VIV nitride complexes to be isolated.

Isolation and Characterization of a Highly Reducing Aqueous Chromium(II) Complex

The highly reducing CrII-(1,3-propylenediaminetetraacetate) (CrPDTA) complex (-1.1 V vs SHE) has been isolated from aqueous solution and the solid-state structure is described. The reduced CrIIPDTA complex is characterized by single-crystal X-ray diffraction, elemental analysis, infrared spectroscopy, UV-vis spectroscopy, magnetic moment, and density functional theory calculations. The concentration profile, state of charge, and pH of CrPDTA electrolyte were monitored in a flow battery system in situ by absorption spectroscopy and a pH probe. The stability of CrIIPDTA in aqueous environments is demonstrated by the ability to isolate CaCrPDTA, despite the common misconception that water spontaneously evolves hydrogen at such potentials. The reduced CrIIPDTA prevents water from coordinating to the metal center by maintaining the same coordinatively saturated pseudo-octahedral structure as the oxidized CrIIIPDTA, despite experiencing an increased geometric strain from a Jahn-Teller distortion of the high-spin CrII ion. The important difference between solvent reactivity and solvent thermodynamic window is examined by comparing the electrochemical behavior of the reduced species of CrPDTA in various organic solvents to its behavior in aqueous solution. When examined in tetrahydrofuran (THF), the reduction potential of CrPDTA is observed to be -1.19 V vs cobaltocene (-2.52 V vs ferrocene). Reduced CrPDTA in aqueous solution is also exposed to atmospheric O2 without exhibiting any decomposition of the Cr(III) or Cr(II) species. The techniques detailed provide a higher standard method of characterization for flow battery electrolyte species.

FeIII in a high-spin state in bis(5-bromosalicylaldehyde 4-ethylthiosemicarbazonato-κ3O,N1,S)ferrate(III) nitrate monohydrate, the first example of such a cationic FeIII complex unit.

The synthesis and crystal structure (100 K) of the title compound, [Fe(C10H11BrN3OS)2]NO3·H2O, is reported. The asymmetric unit consists of an octahedral [FeIII(HL)2]+ cation, where HL- is H-5-Br-thsa-Et or 5-bromosalicylaldehyde 4-ethylthiosemicarbazonate(1-) {systematic name: 4-bromo-2-[(4-ethylthiosemicarbazidoidene)methyl]phenolate}, a nitrate anion and a noncoordinated water molecule. Each HL- ligand binds via the thione S, the imine N and the phenolate O atom, resulting in an FeIIIS2N2O2 chromophore. The ligands are orientated in two perpendicular planes, with the O and S atoms in cis and the N atoms in trans positions. This [Fe(HL)2](anion)·H2O compound contains the first known cationic FeIII entity containing two salicylaldehyde thiosemicarbazone derivatives. The FeIII ion is in the high-spin state at 100 K. In addition, a comparative IR spectroscopic study of the free ligand and the ferric complex is presented, demonstrating that such an analysis provides a quick identification of the degree of deprotonation and the coordination mode of the ligand in this class of metal compounds. The variable-temperature magnetic susceptibility measurements (5-320 K) are consistent with the presence of a high-spin FeIII ion with a zero-field splitting D= 0.439 (1) cm-1.

Manipulating electron redistribution to achieve electronic pyroelectricity in molecular [FeCo] crystals

Pyroelectricity plays a crucial role in modern sensors and energy conversion devices. However, obtaining materials with large and nearly constant pyroelectric coefficients over a wide temperature range for practical uses remains a formidable challenge. Attempting to discover a solution to this obstacle, we combined molecular design of labile electronic structure with the crystal engineering of the molecular orientation in lattice. This combination results in electronic pyroelectricity of purely molecular origin. Here, we report a polar crystal of an [FeCo] dinuclear complex exhibiting a peculiar pyroelectric behavior (a substantial sharp pyroelectric current peak and an unusual continuous pyroelectric current at higher temperatures) which is caused by a combination of Fe spin crossover (SCO) and electron transfer between the high-spin Fe ion and redox-active ligand, namely valence tautomerism (VT). As a result, temperature dependence of the pyroelectric behavior reported here is opposite from conventional ferroelectrics and originates from a transition between three distinct electronic structures. The obtained pyroelectric coefficient is comparable to that of polyvinylidene difluoride at room temperature.

Synthesis, Crystal Structure and Magnetic Properties of 1D Chain Complexes Based on Azo Carboxylate Oxime Ligand

Two carboxylate-bridged one-dimensional chain complexes, {[MnII(MeOH)2][FeIII(L)2]2}n (1) and {[MnII(DMF)2][MnIII(L)2]2·DMF}n (2) [H2L = ((2-carboxyphenyl)azo)-benzaldoxime], containing a low-spin [FeIII(L)2]− or [MnIII(L)2]− unit were synthesized. Magnetic measurements show that the adjacent high-spin MnII and low-spin MIII ions display weak antiferromagnetic coupling via the syn–anti carboxyl bridges, with J = −0.066(2) cm−1 for complex 1 and J = −0.274(2) cm−1 for complex 2.

Substituent effect on metal-to-metal charge transfer behavior of cyanide-bridged {Fe2Co2} square

Using different cyanometallate building blocks ([(TpR)Fe(CN)3]–) and pyrazino[2, 3-f][1,10]phenanthroline (dpq) ligand, three cyanide–bridged {Fe2Co2} tetranuclear complexes {[(Tp*)Fe(CN)3]2[Co(dpq)2]2[ClO4]2}·4H2O (1), {[(Tp4-Me)Fe(CN)3]2[Co(dpq)2]2[ClO4]2}·4H2O (2) and {[(Tp)Fe(CN)3]2[Co(dpq)2]2 [(Tp)Fe(CN)3][ClO4]}·2CH3OH·5H2O (3) were synthesized. Single crystal X-ray diffraction study showed that all compounds shared the similar square tetranuclear structures. Magnetic study indicated that 1 maintained the high-spin state for the CoII ion in the whole temperature range, and showed the ferromagnetic interaction between low-spin FeIII and high-spin CoII ions. In contrast, 2 and 3 showed thermally and photoinduced intramolecular metal-to-metal charge transfer (MMCT) between the FeII/III and CoII/III redox pairs. The comparison study suggested that the electronic and steric effects of the substituents in cyanometallate building blocks as well as the intermolecular interactions can affect the redox potential of metal ions, thereby resulting in different MMCT properties.

Stabilization of high-spin Mn ions in tetra-pyrrolic configuration on copper

By means of Mn-Cu transmetalation, we incorporated Mn atoms in an array of TCNQ (7,7,8,8-tetracyanoquinodimethane) grown on Cu(100), forming a long range ordered and commensurate metal–organic coordination network (MOCN). Preliminary Sn alloying of the Cu(100) surface allowed us to control the degree of substrate reactivity, thus preventing the chemical interaction of the Mn-TCNQ MOCN with the substrate. Mn2+ ions are stabilized in an artificial tetra-pyrrolic coordination, which mimics the macrocyle configuration of Mn-phthalocyanines/porphyrins. X-ray absorption spectroscopy at the Mn L2,3-edge indicates that the Mn ions are in a high-spin state (S = 5/2), in agreement with DFT + U calculations which also shows that the electronic structure of this Mn-TCNQ MOCN is very similar to that of the corresponding unsupported MOCN.

Single crystal growth, structural characterization and magnetic properties study of an antiferromagnetic trinuclear iron(III) acetate complex with uncoordinated hexamine

Structural characterization of novel Fe(III) basic acetate with 1,3,5,7-tetraazaadamantane (hexamine – HEX), [Fe3(μ3-O)(OAc)6(H2O)3)](NO3)(HEX)2(H2O)5] (1), revealed a molecular structure typical for Fe(III) basic carboxylates, with a triangular array formed by three iron atoms being equilateral and with an uncoordinated hexamine molecule and nitrate anion present in the crystal structure. Despite the hexamine molecule being uncoordinated, it plays a crucial role in the formation of a supramolecular network. The magnetic properties of the compound were characterized by magnetic susceptibility, Mössbauer and EPR spectroscopy. These studies indicate the presence of high-spin iron ions in +3 oxidation state with non-Curie-like behaviour. A small room temperature value of the effective magnetic moment and a decrease of the product χT with decreasing temperature both speak in favour of antiferromagnetic interactions between the three individual Fe(III) ions of complex 1 with a total ground state spin of St = 1/2 per trinuclear cluster. EPR spectroscopy confirmed the formation of a St = 1/2 ground state, but also suggested the presence of weak intermolecular exchange interactions between two (or more) clusters of neighbouring molecules. The temperature-dependent Mössbauer spectra show a slowing-down of the fast spin-lattice relaxation rates of the paramagnetic Fe(III) ion below about 60 K, however, yet no static spin regime is reached down to 3.6 K.

Iron(III) Complexes Based on N-Benzylidene-2-Hydroxy-3,5-Di-tert-Butylaniline

Five-coordinate iron(III) complexes, (ImPh)2FeX (X = Cl (I), Br (II), I (III), N3 (IV)) containing two bidentate Schiff bases (N-benzylidene-2-hydroxy-3,5-di-tert-butylaniline (ImPh)H) and a halogen atom/azide group in the coordination sphere were synthesized and characterized in detail. According to the magnetic susceptibility measurements for polycrystalline samples of I–IV and Mossbauer spectroscopy data in the 2–300 K range, the complexes contain a high-spin metal ion (HS Fe3+, d5, SFe = 5/2). Compounds I–IV are stable in the crystalline state in the absence of oxygen or air moisture; however, in solution, they undergo symmetrization, resulting in the formation of the tris-ligand complex (ImPh)3Fe (V), which was also synthesized by the reaction (ImPh)H and FeCl3 (3 : 1). Unlike five-coordinate complexes I–IV, six-coordinate complex V contains low-spin iron(III) ion (LS Fe3+, d5, SFe = 1/2). The molecular structure of I was determined by X-ray diffraction (CIF file CCDC no. 1996527).

Competing antiferromagnetic-ferromagnetic states in a d7 Kitaev honeycomb magnet.

The Kitaev model is a rare example of an analytically solvable and physically instantiable Hamiltonian yielding a topological quantum spin liquid ground state. Here we report signatures of Kitaev spin liquid physics in the honeycomb magnet Li3Co2SbO6, built of high-spin (Co2+) ions, in contrast to the more typical low-spin electron configurations in the presence of large spin-orbit coupling. Neutron powder diffraction measurements, heat capacity, and magnetization studies support the development of a long-range antiferromagnetic order space group of , below at . The magnetic entropy recovered between and 50 K is estimated to be , in good agreement with the value expected for systems close to a Kitaev quantum spin liquid state. The temperature-dependent magnetic order parameter demonstrates a value of 0.19(3), consistent with XY anisotropy and in-plane ordering, with Ising-like interactions between layers. Further, we observe a spin-flop-driven crossover to ferromagnetic order with space group of under an applied magnetic field of at . Magnetic structure analysis demonstrates these magnetic states are competing at finite applied magnetic fields even below the spin-flop transition. Both the compass model, a quantitative comparison of the specific heat of Li3Co2SbO6, and related honeycomb cobaltates to the anisotropic Kitaev model further support proximity to a Kitaev spin liquid state. This material demonstrates the rich playground of high-spin systems for spin liquid candidates and complements known Ir- and Ru-based materials.

High-sensitivity Gd3+-Gd3+ EPR distance measurements that eliminate artefacts seen at short distances.

Gadolinium complexes are attracting increasing attention as spin labels for EPR dipolar distance measurements in biomolecules and particularly for in-cell measurements. It has been shown that flip-flop transitions within the central transition of the high-spin Gd ion can introduce artefacts in dipolar distance measurements, particularly when measuring distances less than 3 nm. Previous work has shown some reduction of these artefacts through increasing the frequency separation between the two frequencies required for the double electron-electron resonance (DEER) experiment. Here we use a high-power (1 kW), wideband, non-resonant system operating at 94 GHz to evaluate DEER measurement protocols using two stiff Gd(III) rulers, consisting of two -Gd-PyMTA complexes, with separations of 2.1 nm and 6.0 nm, respectively. We show that by avoiding thecentral transition completely, and placing both the pump and the observer pulses on either side of the central transition, we can now observe apparently artefact-free spectra and narrow distance distributions, even for a Gd-Gd distance of 2.1 nm.Importantly we still maintain excellent signal-to-noise ratio and relatively high modulation depths. These results have implications for in-cell EPR measurements at naturally occurring biomolecule concentrations.

High-Spin Paramagnetic Ions as Qubits and Qutrits for Quantum Computations

Paramagnetic ions having two electrons and spin S = 1 in zero magnetic field are proposed for new physical performance of elementary quantum computing operations by pulsed manipulations with electron spins. For this purpose, a new type of microwave pulses with variable phases and different polarizations are shown can be used. Such pulses are able to induce different transitions between ion spin states. Some of those transitions are described by operators similar to quantum computing operators. To describe the effects of such pulses on hig-spin ions, a new way to represent exponential operators as polynomials of the Pauli matrices is proposed.

Pentacoordinated manganese(III) bis-o-iminobenzosemiquinonates: Looking for spin-crossover phenomenon

A series of pentacoordinated bis-o-iminobenzosemiquinonato manganese(III) complexes with general formula (imSQR)2MnX (where imSQR – is a radical anion of corresponding o-iminobenzoquinone/o-aminophenol, X – halogen, azide, isocyanate) has been synthesized and characterized in detail. 4,6-Di‑tert‑butyl‑N-(2,6-dimethylphenyl)-o-iminobenzoquinone (imQMe), 4,6-di‑tert‑butyl‑N-(2-methoxyphenyl)-o-aminophenol (APOMeH2), and 4,6-di‑tert‑butyl‑N-(2-trifluoromethylphenyl)-o-aminophenol (APCF3H2) were used as initial substances to provide both sterical and electronic variety of paramagnetic ligands in (imSQR)2MnX complexes (R = Me, X = Cl (1), Br (2), I (3), N3 (4), NCO (5); R = OMe, X =Br (7), I (8), N3 (9); R = CF3, X = Cl (10), Br (11), I (12), N3 (13), NCO (14)). Molecular structures of 2, 9–11 have been established by single-crystal X-ray analysis. The increasing of the sterical bulkiness of imSQR ligands leads to the significant distortion of coordination polyhedrons from the almost ideal square pyramid (SP) for 10 and 11 to significantly distorted one towards trigonal bipyramid (TB) for 9 and 2. According to the magnetic susceptibility measurements of polycrystalline samples of 1–14, strong antiferromagnetic metal-ligand spin interactions between unpaired electrons of high-spin MnIII ion (h.s., d4, SMn = 2) and two imSQ ligands (SR = 1/2) lead to observed triplet ground state in all complexes.

Nickel(II) and Cobalt(III) bis(dioxolene) complexes with di(2-pyridyl)imine ligands: Synthesis and magnetic properties

Here the synthesis, the molecular structure and the magnetic propertiesof four novel six-coordinated bis-dioxolene nickel and cobalt complexes with various di(pyridyl)imines as ancillary N-donor ligands is discussed. Despite the analogous composition the obtained compounds show different charge distribution dependently on the nature of complexing metal. Bis-o-semiquinonato nickel(II) complexes demonstrate the strong ferromagnetic exchange interaction between unpaired electrons of the high-spin nickel ion and anion-radical ligands. Cobalt complex containing naphtyl-substituted ancillary ligand demonstrates the proceeding of solid-state redox-isomeric transformation at temperatures above 220 K.

Electronic Structure and Magnetic Properties of a Titanium(II) Coordination Complex.

Stable coordination complexes of TiII (3d2) are relatively uncommon, but are of interest as synthons for low oxidation state titanium complexes for application as potential catalysts and reagents for organic synthesis. Specifically, high-spin TiII ions supported by redox-inactive ligands are still quite rare due to the reducing power of this soft ion. Among such TiII complexes is trans-[TiCl2(tmeda)2], where tmeda = N,N,N',N'-tetramethylethane-1,2-diamine. This complex was first reported by Gambarotta and co-workers almost 30 years ago, but it was not spectroscopically characterized and theoretical investigation by quantum chemical theory (QCT) was not feasible at that time. As part of our interest in low oxidation state early transition metal complexes, we have revisited this complex and report a modified synthesis and a low temperature (100 K) crystal structure that differs slightly from that originally reported at ambient temperature. We have used magnetometry, high-frequency and -field EPR (HFEPR), and variable-temperature variable-field magnetic circular dichroism (VTVH-MCD) spectroscopies to characterize trans-[TiCl2(tmeda)2]. These techniques yield the following S = 1 spin Hamiltonian parameters for the complex: D = -5.23(1) cm-1, E = -0.88(1) cm-1, (E/D = 0.17), g = [1.86(1), 1.94(2), 1.77(1)]. This information, in combination with electronic transitions from MCD, was used as input for both classical ligand-field theory (LFT) and detailed QCT studies, the latter including both density functional theory (DFT) and ab initio methods. These computational methods are seldom applied to paramagnetic early transition metal complexes, particularly those with S > 1/2. Our studies provide a complete picture of the electronic structure of this complex that can be put into context with the few other high-spin and mononuclear TiII species characterized to date.