Temperature-independent Paramagnetism Research Articles

Cerium(iv) complexes with guanidinate ligands: intense colors and anomalous electronic structures.

A series of cerium(iv) mixed-ligand guanidinate–amide complexes, {[(Me3Si)2NC(NiPr)2]xCeIV[N(SiMe3)2]3−x}+ (x = 0–3), was prepared by chemical oxidation of the corresponding cerium(iii) complexes, where x = 1 and 2 represent novel complexes. The Ce(iv) complexes exhibited a range of intense colors, including red, black, cyan, and green. Notably, increasing the number of the guanidinate ligands from zero to three resulted in significant redshift of the absorption bands from 503 nm (2.48 eV) to 785 nm (1.58 eV) in THF. X-ray absorption near edge structure (XANES) spectra indicated increasing f occupancy (nf) with more guanidinate ligands, and revealed the multiconfigurational ground states for all Ce(iv) complexes. Cyclic voltammetry experiments demonstrated less stabilization of the Ce(iv) oxidation state with more guanidinate ligands. Moreover, the Ce(iv) tris(guanidinate) complex exhibited temperature independent paramagnetism (TIP) arising from the small energy gap between the ground- and excited states with considerable magnetic moments. Computational analysis suggested that the origin of the low energy absorption bands was a charge transfer between guanidinate π orbitals that were close in energy to the unoccupied Ce 4f orbitals. However, the incorporation of sterically hindered guanidinate ligands inhibited optimal overlaps between Ce 5d and ligand N 2p orbitals. As a result, there was an overall decrease of ligand-to-metal donation and a less stabilized Ce(iv) oxidation state, while at the same time, more of the donated electron density ended up in the 4f shell. The results indicate that incorporating guanidinate ligands into Ce(iv) complexes gives rise to intense charge transfer bands and noteworthy electronic structures, providing insights into the stabilization of tetravalent lanthanide oxidation states.

Correlated electron metal properties of the honeycomb ruthenate Na2RuO3

We report the synthesis and characterisation of polycrystalline Na$_2$RuO$_3$, a layered material in which the Ru$^{4+}$ ($4d^4$ configuration) form a honeycomb lattice. The optimal synthesis condition was found to produce a nearly ordered Na$_2$RuO$_3$ ($C2/c$ phase), as assessed from the refinement of the time-of-flight neutron powder diffraction. Magnetic susceptibility measurements reveal a large temperature-independent Pauli paramagnetism ($\chi_0 \sim 1.42(2)\times10^{-3}$ emu/mol Oe) with no evidence of magnetic ordering down to 1.5 K, and with an absence of dynamic magnetic correlations, as evidenced by neutron scattering spectroscopy. The intrinsic susceptibility ($\chi_0$) together with the Sommerfeld coeficient of $\gamma=11.7(2)$ mJ/Ru mol K$^2$ estimated from heat capacity measurements, gives an enhanced Wilson ratio of $R_W\approx8.9(1)$, suggesting that magnetic correlations may be present in this material. While transport measurements on pressed pellets show nonmetallic behaviour, photoemission spectrocopy indicate a small but finite density of states at the Fermi energy, suggesting that the bulk material is metallic. Except for resistivity measurements, which may have been compromised by near surface and interface effects, all other probes indicate that Na$_2$RuO$_3$ is a moderately correlated electron metal. Our results thus stand in contrast to earlier reports that Na$_2$RuO$_3$ is an antiferromagnetic insulator at low temperatures.

Corrigendum: Entrapment of a Pseudo-Tetrahedral CoII Center by Thioether Sulfur Bound {Co2 (μ-L)} Fragments: Synthesis, Field-Induced Single-Ion Magnetism and Catechol Oxidase Mimicking Activity.

It has come to the attention of the authors that Figure 6, the values of effective magnetic moments for complexes 1 and 2, giso, E/D values in Abstract section and in the Magnetic properties sections, giso and E/D values in Table 1, and D value for complex 2 in Conclusions section were changed mistakenly in the final stage of manuscript preparation. The data published in Figure 6 reveal the results obtained for older measurement on different batches of the complexes. The correct values, corresponding to the results obtained for the same batches of complexes for which the DC and AC magnetic measurements were done, are presented below. These mistakes do not affect the integrity of the research and overall conclusions of the published paper. The corrected Figure 6 and corresponding text are given below. Magnetic properties. Investigation of the magnetic features of complexes 1 and 2 proceeded using a PPMS device on which the temperature (1.9–300 K) and field (0–9 T) dependent magnetic data were obtained (Figure 6). Figure 6 Temperature dependence of the effective magnetic moment (inset: temperature dependence of the molar magnetic susceptibility) for complexes 1 and 2 (Left). The isothermal magnetizations measured in the range of B=0–9 T and at T=2, 5 and 10 K (Right). The magnetic properties of the complexes are primarily due to the presence of central tetrahedral CoII ion since octahedral LS-CoIII ions are diamagnetic. The value of effective magnetic moment (μeff) of complex 1 at 300 K is 3.5 μB, slightly lower than the spin-only value of 3.9 μB for S=3/2, g=2.0. Thereafter upon cooling the μeff value raises slightly up to ca 75 K and then, it drops sharply to a minimum at 1.9 K, where it adopts the value of 3.2 μB. In the case of complex 2, the μeff value at 300 K is 5.0 μB which is again much higher that the calculated value for isotropic S=3/2 spin. It decreases gradually upon cooling up to ca 50 K and then, it declines sharply to a minimum at 4.4 K reaching the value of 4.2 μB. The high μeff value at 300 K indicates considerable contribution of a spin-orbit coupling to the ground state in the complex 2. Isothermal magnetization experiments (Figure 6) for 1 and 2 in the applied field range of B=0–9 T at different constant temperatures T=2, 5 and 10 K reveal that the magnetization does not show saturation suggesting the presence of magnetic anisotropy. To extract the parameters affected by magnetic anisotropy arising from crystal field effects (g, D), both the susceptibility and magnetization data were fitted simultaneously. The best fit parameters were calculated using the PHI program package[26] for S=3/2 and they are as follows: giso=2.05, D=−23.6 cm−1, E/D=0, zJ/hc=0 cm−1, χTIP=−13.0×10−4 cm3 mol−1 for 1 and giso=2.61, D=−24.3 cm−1, E/D=0.01, zJ/hc=0.05 cm−1, χTIP=2.0×10−4 cm3 mol−1 for 2. The presence of temperature-independent paramagnetism (TIP) term accounts for the four surrounding CoIII ions. The observed D values for 1 and 2 are relatively close compared to those (−31.31 cm−1 and −21.88 cm−1) obtained in our previous investigations with complexes having similar molecular structures.[10] The authors wish to emphasize that with these corrections, the reported ZFS parameters relevant for the discussion of single molecule magnetism (i.e. the D values) did not change at all and the overall conclusions published in the original version of the article are not affected.

Os4+ Instability in the Pyrochlore Structure: Tl2-xBixOs2O7-y.

Osmium-containing oxides are rare due to the difficulty in stabilizing complex structures with a fixed stoichiometry and metastability of the phases. Bismuth-substituted thallium osmate pyrochlore samples, Tl2-xBixOs2O7-y, were synthesized using solid-state reactions where the solubility limit was found to be approximately x = 1.4. Members of this solid solution were characterized by their structural, electronic, magnetic, and thermal properties to understand the influence of Bi3+ substitution on the ground state. The Os-containing pyrochlores crystallize in the ideal cubic pyrochlore structure (Fd3m), and the lattice parameter a was found to slightly increase as a function of Bi content. A possible interplay between structure and cation valence states was explored using both neutron powder diffraction and X-ray absorption spectroscopy, suggesting that a combination of Os4+/Os5+ and Tl1+/Tl3+ mixed valency throughout the solid solution allows for the stabilization of the pyrochlore structure. The system is metallic for the entire solid solution and predominantly exhibits temperature-independent paramagnetism. Specific heat measurements show an enhanced Sommerfeld coefficient, a possible flat-band signature. This system gave insight into the bonding preferences of Os, indicating a dependence on high oxidation states and mixed valence for the stability of complex structures.

Pauli Paramagnetism of Stable Analogues of Pernigraniline Salt Featuring Ladder-Type Constitution.

Polyaniline derivatives represent one of the most widely used classes of conductive polymers. The fundamentally important electronic properties of pernigraniline salts, the fully oxidized and acid-doped derivatives of polyanilines, however, are still not well-understood due to their poor stability and configurational uncertainty. To address these issues and to synthetically access stable analogues of pernigraniline salts, ladder-type constitution was imparted into a series of model oligomer analogues with rigid backbones constituted by up to 27 fused rings. The syntheses were achieved through iterative cross-coupling reactions followed by cyclization and oxidation. In contrast to their unstable non-ladder-type counterparts, these ladder-type pernigraniline-like molecules all adopt a well-defined all-trans configuration and demonstrate an excellent chemical stability after protonation, rendering it possible to reveal the intrinsic electronic and magnetic properties of molecules resembling pernigraniline. Protonated salts of these oligomers feature a significant diradicaloid open-shell resonance contribution. A dominant temperature-independent Pauli paramagnetism was observed in the solid state, an indication of the delocalization nature of the polarons in ladder-type analogues of pernigraniline salt.

Dinuclear and Mononuclear Rhenium Coordination Compounds upon Employment of a Schiff-Base Triol Ligand: Structural, Magnetic, and Computational Studies.

The 1:1 reaction of trans-[ReIIICl3(PPh3)2(MeCN)] with 2-(β-naphthalideneamino)-2-hydroxymethyl-1-propanol, H3L, in toluene gave the dinuclear complex [ReIII2Cl4(HL)(PPh3)]·2C7H8 (1·2C7H8), while the 1:2 reaction led to the formation of complex [ReIVCl2(HL)(PPh3)] (2). In both species, the Schiff-base ligand exists in its doubly deprotonated form, HL2-, forming chelate rings around the metallic centers. In addition, 1·2C7H8 displays a unique triple metal-to-metal bond between the two trivalent rhenium ions separated at a 2.229(1) Å bond distance, while in complex [ReIVCl2(HL)(PPh3)] (2) the two aromatic ligands, HL2- and PPh3, occupy axial positions, with the terminal Cl- ions in the trans position. Investigation of the magnetic properties revealed a Curie paramagnetic behavior ( S = 1/2) with a pronounced temperature independent paramagnetism (TIP) for 1·2C7H8 and 2. Both the geometry and the electronic structure of both compounds have been studied by means of density functional theory (DFT) calculations, confirming the triplet and doublet spin ground state of the complexes and furthermore establishing an electron-rich σ2π4δ1δ*1 bond order of 3 for 1·2C7H8. In addition, the absorption spectrum of 1·2C7H8 in CH2Cl2 was simulated by means of DFT calculations and is in excellent agreement with both the crystallographic and theoretical studies. Complex 1·2C7H8 is the first dinuclear rhenium complex with a triple metal-metal bond between trivalent rhenium centers.

13C NMR Shifts as an Indicator of U-C Bond Covalency in Uranium(VI) Acetylide Complexes: An Experimental and Computational Study.

A series of uranium(VI)-acetylide complexes of the general formula UVI(O)(C≡C-C6H4-R)[N(SiMe3)2]3, with variation of the para substituent (R = NMe2, OMe, Me, Ph, H, Cl) on the aryl(acetylide) ring, was prepared. These compounds were analyzed by 13C NMR spectroscopy, which showed that the acetylide carbon bound to the uranium(VI) center, U- C≡C-Ar, was shifted strongly downfield, with δ(13C) values ranging from 392.1 to 409.7 ppm for Cl and NMe2 substituted complexes, respectively. These extreme high-frequency 13C resonances are attributed to large negative paramagnetic (σpara) and relativistic spin-orbit (σSO) shielding contributions, associated with extensive U(5f) and C(2s) orbital contributions to the U-C bonding in title complexes. The trend in the 13C chemical shift of the terminal acetylide carbon is opposite that observed in the series of parent (aryl)acetylenes, due to shielding effects of the para substituent. The 13C chemical shifts of the acetylide carbon instead correlate with DFT computed U-C bond lengths and corresponding QTAIM delocalization indices or Wiberg bond orders. SQUID magnetic susceptibility measurements were indicative of the Van Vleck temperature independent paramagnetism (TIP) of the uranium(VI) complexes, suggesting a magnetic field-induced mixing of the singlet ground-state (f0) of the U(VI) ion with low-lying (thermally inaccessible) paramagnetic excited states (involved also in the perturbation-theoretical treatment of the unusually large paramagnetic and SO contributions to the 13C shifts). Thus, together with reported data, we demonstrate that the sensitive 13C NMR shifts serve as a direct, simple, and accessible measure of uranium(VI)-carbon bond covalency.

Cerium Tetrakis(tropolonate) and Cerium Tetrakis(acetylacetonate) Are Not Diamagnetic but Temperature-Independent Paramagnets.

A new synthesis of cerium tetrakis(tropolonate), Ce(trop)4, where trop is deprotonated 2-hydroxy-2,4,6-cycloheptatrienone) or Ce(O2C7H5)4, is developed that results in dark-purple crystals whose X-ray crystal structure shows that the geometry of the eight-coordinate compound closely resembles a D2 d dodecahedron, based on shape parameters. The magnetic susceptibility as a function of the temperature (4-300 K) shows that it is a temperature-independent paramagnet, χ = 1.2(3) × 10-4 emu/mol, and the LIII-edge X-ray absorption near-edge structure spectrum shows that the molecule is multiconfigurational, comprised of a f1:f0 configuration mixture in a 50:50 ratio. Ce(acac)4 and Ce(tmtaa)2 (where acac is acetylacetonate and tmtaaH2 is tetramethyldibenzotetraaza[14]annulene) have similar physical properties, as does the solid-state compound CeO2. The concept is advanced that trop-, acac-, tmtaa2-, cot2-, and O2- are redox-active ligands that function as electron donors, rendering the classification of these compounds according to their oxidation numbers misleading because their magnetic susceptibilities, χ, are positive and their effective magnetic moments, μeff, lie in the range of 0.1-0.7 μB at 300 K.

The Smaller the Better: Hosting Trivalent Rare-Earth Guests in Cu–P Clathrate Cages

Summary The most striking difference between the trivalent rare-earth cations and their alkali and alkaline-earth peers is the presence of localized 4 f electrons. Placing trivalent rare-earth cations inside fullerene molecules or in between blocks of intermetallics has given rise to a plethora of fascinating properties and materials. A long-sought-after yet undiscovered material is a semiconducting compound with rare-earth cations situated inside the oversized polyhedral cages of a three-dimensional framework. In this work, we present a synthesis of unconventional clathrates, Ba 8−x R x Cu 16 P 30 , with the smallest pentagonal dodecahedral cages encapsulating La 3+ and Ce 3+ . Their composition and crystal structure were unambiguously determined by a combination of synchrotron powder diffraction, time-of-flight neutron powder diffraction, scanning transmission electron microscopy, and electron energy-loss spectroscopy. Our quantum-mechanical calculations and experimental characterizations show that the incorporation of the rare-earth cations significantly enhances hole mobility and reduces hole concentration, resulting in a drastic (700%) increase in the thermoelectric performance.

Physical properties of TiMn2 and interaction with refractory TiN (system Ti-Mn-N)

Mechanical (elastic) properties have been derived for polycristalline TiMn2 from micro-indentation and thermal expansion measurements. With a room temperature (RT) Vicker's hardness of ∼11 GPa, TiMn2 is a rather hard intermetallic material. The elastic modulus is E = 217 ± 4 GPa at RT. Physical properties (from 1.8 K to 300 K) including specific heat, electrical resistivity and magnetic susceptibility reveal temperature independent paramagnetism and metallic conductivity consistent with a Bloch-Grüneisen behavior.Based on experimental data (X-ray powder diffraction, metallography, SEM and EMPA on 30 alloys prepared by various methods employing arc melting, powder reaction sintering in closed crucibles as well as nitriding binary master alloys in 105 Pa nitrogen gas) phase relations in the ternary system Ti-Mn-N have been established and calculated for the isothermal section at 900 °C. The thermodynamic modelling relies on existing thermodynamic assessments of the Mn-N and Ti-N binary systems and on our recent modelling of the Ti-Mn system, which is characterized by a significantly higher thermodynamic stability of the C14-type Laves phase Ti1-xMn2+x than hitherto assumed in the literature. It is this higher stability, which is consistent with the experimental phase triangulation in Ti-Mn-N: as the most important consequence of the higher stability of Ti1-xMn2+x, compatibility exists between the only two congruently melting compounds Ti1-xMn2+x and TiN1-x. The high melting refractory solution TiN1-x dominates the liquidus surface pushing all monovariant melting lines close to the Ti-Mn binary.

Puzzling Lack of Temperature Dependence of the PuO2 Magnetic Susceptibility Explained According to Ab Initio Wave Function Calculations.

The electronic structure and the magnetic properties of solid PuO2 are investigated by wave function theory calculations, using a relativistic complete active space (CAS) approach including spin-orbit coupling. The experimental magnetic susceptibility is well reproduced by calculations for an embedded PuO812- cluster model. The calculations indicate that the surprising lack of temperature dependence of the magnetic susceptibility χ of solid PuO2 can be rationalized based on the properties of a single Pu4+ ion in the cubic ligand field of the surrounding oxygen ions. Below ∼300 K, the only populated state is the nonmagnetic ground state, leading to standard temperature-independent paramagnetism (TIP). Above 300 K, there is an almost perfect cancellation of temperature-dependent contributions to χ that depends delicately on the mixing of ion levels in the electronic states, their relative energies, and the magnetic coupling between them.

Titanium(III) Member of the Family of Trigonal Building Blocks with Scorpionate and Cyanide Ligands.

The titanium(III) cyanide compound [Et4N][Tp*Ti(CN)3] ([Et4N] = tetraethylamonium; Tp* = 3,5-dimethyltrispyrazolylhydroborate) is reported, which exhibits a trigonally distorted geometry. Magnetic data and ab initio calculations verified that the molecule is an S = 1/2 paramagnet and that it exhibits significant temperature-independent paramagnetism.

A square-planar osmium(ii) complex.

Reduction of the pincer complex [OsIIICl2(PNP)] (PNP = N(CHCHPtBu2)2) affords the isolation and full characterization of an osmium(ii) complex with square-planar coordination geometry, i.e. [OsIICl(PNP)]. Spectroscopic, structural and magnetic data in combination with multireference computations indicate strong temperature independent paramagnetism, which arises from an energetically well separated ground state that mixes with excited states through spin-orbit coupling.

A new Mo(iv) complex with the pentadentate (N3O2) Schiff-base ligand: the first non-cyanide pentagonal-bipyramidal paramagnetic 4d complex.

A heptacoordinate complex [MoIV(DAPBH)Cl2] (H2DAPBH is 1,1'-(pyridine-2,6-diyl)bis(ethan-1-yl-1-ylidene)dibenzohydrazine) has been synthesized and characterized structurally and magnetically. It exhibits a slightly distorted pentagonal bipyramidal geometry and reveals paramagnetic behaviour resulting from two unpaired electrons (S = 1) with large positive zero-field splitting (D = +50 cm-1) and pronounced temperature-independent paramagnetism.

Low spin Fe(II) complexes formed of monosubstitued 2,6-bis(2-benzimidazolyl)pyridine ligands

Five ligands as monosubstituted derivatives of the basic skeleton of 2,6-bis(2-benzimidazyl)pyridine were synthesized, and characterized by NMR and IR spectra along with the X-ray structure analysis. Their complexation gave a set of hexacoordinate Fe(II) complexes showing predominantly the diamagnetism until ambient temperature. Some temperature-independent paramagnetism along with an onset of the spin transition is also detected.

Anion-Directed Copper(II) Metallocages, Coordination Chain, and Complex Double Salt: Structures, Magnetic Properties, EPR Spectra, and Density Functional Study.

A series of Cu(II) metallo-assemblies showing anion-directed structural variations, including five metallocages [(G(n-) )⊂{Cu2 (Hdpma)4 }]((8-n)+) (A(-) )8-n (G(n-) =NO3 (-) , ClO4 (-) , SiF6 (2-) , BF4 (-) , SO4 (2-) ; A(-) =NO3 (-) , ClO4 (-) , BF4 (-) , CH3 SO4 (-) ; Hdpma=bis(3-pyridylmethyl)ammonium cation), a complex double salt, namely, (H3 dpma)4 (CuCl4 )5 Cl2 , and a coordination chain, namely, [Cu2 (dpma)(OAc)4 ], are reported. The influence of the anion can be explained by its coordinating ability, the affinity of which for the Cu(II) center interferes significantly with metallocage formation, and its shape, which offers host-guest recognition ability to engage in weak metal-anion coordination and hydrogen bonding to the organic ligand, which are responsible for metallocage templation. EPR studies of these metallocages in the powder phase at room temperature and 77 K showed a trend of the g values (g|| >2.10>g⊥ >2.00) indicating a dx2-y2 -based ground state with square-pyramidal geometry for the Cu(II) centers. The magnetism of these metallocages can be interpreted as the result of a combination of relatively small magnetic coupling integrals and a substantial contribution of temperature-independent paramagnetism (TIP). The weak magnetic interaction is corroborated by the results of DFT calculations and the EPR spectra. Availability of the low-lying state for spin population was confirmed by a magnetization study, which revealed a magnetic moment approaching 2Nβ, which would explain the presence of the larger TIP term.

Magneto-structural analysis of metal-orotato coordination complexes based on N[sbnd]H⋯O and O[sbnd]H⋯O supramolecular synthon

Two new supramolecular synthon induced single crystals of metal-orotato complexes of formula [Cu(Orotate)·2H2O]2 (1), [Mn(Orotate)2·2H2O]·2H2O] (2), have been engineered and synthesized by self-assembly of metal salts with orotic acid in presence of 25% ammonia solution. Although both complexes crystallize in similar crystal system and different coordination geometries [(square planar (1), octahedral (2)] but identical synthon patterns recur after complex formation. NH⋯O, OH⋯O synthons were the only artifact for both the hydrogen bonded metal–organic architecture. X-ray structural analysis, EPR, temperature independent paramagnetism (TIP) analysis, have been discussed. DFT calculation is used to rationalize the magnetic behavior of both the complexes. These calculations underline the pathway of magnetic exchange interactions through NH⋯O, OH⋯O supramolecular synthons and confirm, that the magnetic interactions propagate through such contacts in complex 1 and 2.

State of atoms and interatomic interactions in perovskite-like oxides: XXXIV. State of europium atoms and exchange interactions in La1–y Eu y AlO3

A series of solid solutions of the La1–y Eu y AlO3 composition was studied by the method of magnetic dilution in the concentration range 1–20 mol % of europium atoms. Europium atoms in the solid solutions were found to take part in the antiferromagnetic superexchange interactions. Magnetic characteristics at the infinite dilution are described as existence of single Eu(III) atoms with a large contribution of Van Vleck’s temperature independent paramagnetism (∼0.001 emu/mol).

Van Vleck paramagnetism of europium oxyhydroxide

Europium oxyhydroxide crystals were synthesized by the flux method. The as-grown crystals were transparent and had a plate-like shape with natural flat surfaces. The powder XRD data were refined by assuming a monoclinic structure of the space group P21/m and lattice parameters of a=0.4346 nm, b=0.3744 nm, c=0.6107 nm, and β=108.62°. The magnetic susceptibility of the EuOOH crystals exhibited typical Van Vleck temperature-independent paramagnetism below 120 K. The calculated susceptibility, based on Van Vleck's theory, agreed with the experimental data to some extent, with the coupling constant λ=458±10 K. The experimental results were in close agreement with the results calculated using a modified formula with λ=505±2 K and a constant term C=4.6×10−4 emu/(mol·Oe).

Magnetic properties and electronic structures of Ar3U(IV)–L Complexes with Ar = C5(CH3)4H(–) or C5H5(–) and L = CH3, NO, and Cl.

Electronic structures and magnetic properties of the U(4+) complexes (C5Me4H)3UNO, (C5Me4H)3UCl, (C5H5)3UCH3, and (C5H5)3UCl are investigated by quantum chemical calculations. On the basis of wave function calculations including spin-orbit (SO) interactions, all complexes have nondegenerate nonmagnetic ground states. However, for L = CH3 and Cl magnetic doublet excited states are very low in energy, rendering the magnetic susceptibility strongly temperature dependent above ca. 50-100 K. In contrast, (C5Me4H)3UNO exhibits temperature-independent paramagnetism even at room temperature. The calculated susceptibilities agree well with available experimental data. An analysis of the ground states and the magnetic behavior is performed using crystal-field (CF) models with parameters extracted from the ab initio calculations, and with the help of natural orbitals contributing to the electron density, generated from scalar relativistic and SO wave functions for the ground states and selected excited states. Electronic g-factors calculated from the CF models agree well with ab initio data. The U-NO bond order in (C5Me4H)3UNO decreases somewhat due to SO coupling, because U-NO bonding π orbitals with strong U 5fπ character mix with nonbonding 5fδ orbitals under the SO interaction. This complex also exhibits pronounced multireference character. All complexes afford U-ligand 5f covalent character.