Record Quantum Tunneling Time in an Air-Stable Exchange-Bias Dysprosium Macrocycle.

In recent years, dysprosium macrocycle single-molecule magnets (SMMs) have received increasing attention due to their excellent air/thermal stability, strong magnetic anisotropy, and rigid molecular skeleton. However, they usually display fast zero-field quantum tunneling of the magnetization (QTM) rate, severely hindering their data storage applications. Herein, we report the design, synthesis, and characterization of an air-stable monodecker didysprosium macrocycle integrating strong single-ion anisotropy, near-perfect local crystal field (CF) symmetry, and efficient exchange bias. These indispensable features enable clear-cut elucidation of the crucial role of very weak antiferromagnetic coupling on magnetization dynamics, creating a prominent SMM with a large effective energy barrier (Ueff) of 670 cm-1, open hysteresis loops at zero field up to 14.9 K, and a record relaxation time of QTM (τQTM), 24281 s, for all known nonradical-bridged lanthanide SMMs.

Iron(III) Carbene Complexes with Tunable Excited State Energies for Photoredox and Upconversion.

Substituting precious elements in luminophores and photocatalysts by abundant first-row transition metals remains a significant challenge, and iron continues to be particularly attractive owing to its high natural abundance and low cost. Most iron complexes known to date face severe limitations due to undesirably efficient deactivation of luminescent and photoredox-active excited states. Two new iron(III) complexes with structurally simple chelate ligands enable straightforward tuning of ground and excited state properties, contrasting recent examples, in which chemical modification had a minor impact. Crude samples feature two luminescence bands strongly reminiscent of a recent iron(III) complex, in which this observation was attributed to dual luminescence, but in our case, there is clear-cut evidence that the higher-energy luminescence stems from an impurity and only the red photoluminescence from a doublet ligand-to-metal charge transfer (2LMCT) excited state is genuine. Photoinduced oxidative and reductive electron transfer reactions with methyl viologen and 10-methylphenothiazine occur with nearly diffusion-limited kinetics. Photocatalytic reactions not previously reported for this compound class, in particular the C-H arylation of diazonium salts and the aerobic hydroxylation of boronic acids, were achieved with low-energy red light excitation. Doublet-triplet energy transfer (DTET) from the luminescent 2LMCT state to an anthracene annihilator permits the proof of principle for triplet-triplet annihilation upconversion based on a molecular iron photosensitizer. These findings are relevant for the development of iron complexes featuring photophysical and photochemical properties competitive with noble-metal-based compounds.

Bifurcation of Excited-State Population Leads to Anti-Kasha Luminescence in a Disulfide-Decorated Organometallic Rhenium Photosensitizer.

We report a rhenium diimine photosensitizer equipped with a peripheral disulfide unit on one of the bipyridine ligands, [Re(CO)3(bpy)(S-Sbpy4,4)]+ (1+, bpy = 2,2'-bipyridine, S-Sbpy4,4 = [1,2]dithiino[3,4-c:6,5-c']dipyridine), showing anti-Kasha luminescence. Steady-state and ultrafast time-resolved spectroscopies complemented by nonadiabatic dynamics simulations are used to disclose its excited-state dynamics. The calculations show that after intersystem crossing the complex evolves to two different triplet minima: a (S-Sbpy4,4)-ligand-centered excited state (3LC) lying at lower energy and a metal-to-(bpy)-ligand charge transfer (3MLCT) state at higher energy, with relative yields of 90% and 10%, respectively. The 3LC state involves local excitation of the disulfide group into the antibonding σ* orbital, leading to significant elongation of the S-S bond. Intriguingly, it is the higher-lying 3MLCT state, which is assigned to display luminescence with a lifetime of 270 ns: a signature of anti-Kasha behavior. This assignment is consistent with an energy barrier ≥ 0.6 eV or negligible electronic coupling, preventing reaction toward the 3LC state after the population is trapped in the 3MLCT state. This study represents a striking example on how elusive excited-state dynamics of transition-metal photosensitizers can be deciphered by synergistic experiments and state-of-the-art calculations. Disulfide functionalization lays the foundation of a new design strategy toward harnessing excess energy in a system for possible bimolecular electron or energy transfer reactivity.

Synthesis and Semi-Synthesis of Alpha-Synuclein: Insight into the Chemical Complexity of Synucleinopathies.

The chemical rules governing protein folding have intrigued generations of researchers for decades. With the advent of artificial intelligence (AI), prediction of protein structure has improved tremendously. However, there is still a level of analysis that is only possible through wet laboratory experiments, especially in respect to the investigation of the pathological effect of mutations and posttranslational modifications (PTMs) on proteins of interest. This requires the availability of pure peptides and proteins in sufficient quantities for biophysical, biochemical, and functional studies. In this context, chemical protein synthesis and semi-synthesis are powerful tools in protein research, which help to enlighten the role of protein modification in the physiology and pathology of proteins. A protein of high interest in the field of biomedicine is alpha-synuclein (aSyn), a protein deeply associated with several devastating neurodegenerative disorders such as Parkinson's disease (PD), dementia with Lewy bodies (DLB), or multiple systems atrophy (MSA). Here, we describe several methods and pathways to synthesize native or modified aSyn, and discuss how these approaches enable us to address pathological mechanisms that may open novel perspectives for therapeutic intervention.

Ferromagnetically Coupled Chromium(III) Dimer Shows Luminescence and Sensitizes Photon Upconversion.

There has been much progress on mononuclear chromium(III) complexes featuring luminescence and photoredox activity, but dinuclear chromium(III) complexes have remained underexplored in these contexts until now. We identified a tridentate chelate ligand able to accommodate both meridional and facial coordination of chromium(III), to either access a mono- or a dinuclear chromium(III) complex depending on reaction conditions. This chelate ligand causes tetragonally distorted primary coordination spheres around chromium(III) in both complexes, entailing comparatively short excited-state lifetimes in the range of 400 to 800 ns in solution at room temperature and making photoluminescence essentially oxygen insensitive. The two chromium(III) ions in the dimer experience ferromagnetic exchange interactions that result in a high spin (S=3) ground state with a coupling constant of +9.3 cm-1. Photoinduced energy transfer from the luminescent ferromagnetically coupled dimer to an anthracene derivative results in sensitized triplet-triplet annihilation upconversion. Based on these proof-of-principle studies, dinuclear chromium(III) complexes seem attractive for the development of fundamentally new types of photophysics and photochemistry enabled by magnetic exchange interactions.

Chromium-Thiolate Complex Undergoing C-S Bond Cleavage.

The cleavage of C-S bonds represents a crucial step in fossil fuel refinement to remove organosulfur impurities. Efforts are required to identify alternatives that can replace the energy-intensive hydrodesulfurization process currently in use. In this context, we have developed a series of bis-thiolato-ligated CrIII complexes supported by the L2- ligand (L2- = 2,2'-bipyridine-6,6'-diyl(bis(1,1-diphenylethanethiolate), one of them displaying desulfurization of one thiolate of the ligand under reducing and acidic conditions at ambient temperature and atmospheric pressure. While only 5-coordinated complexes were previously isolated by reaction of L2- with 3d metal MIII ions, both 5- and 6-coordinated mononuclear complexes have been obtained in the case of CrIII, viz., [CrIIILCl], [CrIIILCl2]-, and [CrIIILCl(CH3CN)]. The investigation of the reactivity of [CrIIILCl(CH3CN)] under reducing conditions led to a dinuclear [CrIII2L2(µ-Cl)(µ-OH)] compound and, in the presence of protons, to the mononuclear CrIII complex [CrIII(LN2S)2]+, where LN2S- is the partially desulfurized form of L2-. A desulfurization mechanism has been proposed involving the release of H2S, as evidenced experimentally.

Hourglass-Shaped Homo- and Heteronuclear Nonanuclear Lanthanide Clusters: Structures, Magnetism, Photoluminescence, and Theoretical Analysis.

Synthesis of nonameric cationic clusters [Dy9(acac)16(µ3-OH)8(µ4-OH)2]OH·6H2O (1), [Dy8Tb (acac)16(µ3-OH)8(µ4-OH)2]OH·2H2O (2), and [Gd9(acac)16(µ3-OH)8(µ4-OH)2]OH·6H2O (3) (acac = acetylacetonate) is reported. The emission spectrum of 1 shows Dy(III) ion characteristic bands assignable to the 4F9/2 → 6HJ (J = 15/2 to 9/2) transitions. Emission due to both Dy(III) and Tb(III) ions is observed for 2 in the visible range, with Tb(III) specific bands appearing due to the 5D4 → 7FJ (J = 6, 4, and 3) transitions. Cluster 3 exhibits a significant magnetocaloric effect (MCE), with -ΔSm values increasing with decrease in temperature and increase in field, reaching -ΔSmmax = 20.98 J kg-1 K-1 at 2 K and 9 T. Isotropic magnetic coupling constants (Js) in 3 derived from density functional theory (DFT) calculations reveal that the exchange interactions are antiferromagnetic and weak. Compound 3 possesses S = 7/2 ground state arising from the central Gd(III) ion along with several nested excited states due to competing antiferromagnetic interactions that yield reasonably large MCE values. Utilizing computed exchange coupling interactions, we have performed ab initio CASSCF/RASSI-SO/POL_ANISO calculations on antiferromagnetic 1 and 2 to estimate the exchange interactions using the Lines model. For 2, Dy(III)···Tb(III) exchange interactions were extracted for the first time and were found to be weakly antiferromagnetically coupled.

Oxygen-Donor Metalloligands Induce Slow Magnetization Relaxation in Zero Field for a Cobalt(II) Complex with {CoO4} Motif.

Most 3d metal-based single-molecule magnets (SMMs) use N-ligands or ligands with even softer donors to impart a particular coordination geometry and increase the zero-field splitting parameter |D|, while complexes with hard O-donor ligands showing slow magnetization relaxation are rare. Here, we report that a diamagnetic NiII complex of a tetradentate ligand featuring two N-heterocyclic carbene and two alkoxide-O donors, [LO,ONi], can serve as a {O,O'}-chelating metalloligand to give a trinuclear complex [(LO,ONi)Co(LO,ONi)](OTf)2 (2) with an elongated tetrahedral {CoIIO4} core, D = -74.3 cm-1, and a spin reversal barrier Ueff = 86.9 cm-1 in the absence of an external dc field. The influence of diamagnetic NiII on the electronic structure of the {CoO4} unit in comparison to [Co(OPh)4]2- (A) has been probed with multireference ab initio calculations. These reveal a contrapolarizing effect of the NiII, which forms stronger metal-alkoxide bonds than the central CoII, inducing a change in ligand field splitting and a 5-fold increase in the magnetic anisotropy in 2 compared to A, with an easy magnetization axis along the Ni-Co-Ni vector. This demonstrates a strategy to enhance the SMM properties of 3d metal complexes with hard O-donors by modulating the ligand field character via the coordination of diamagnetic ions and the benefit of robust metalloligands in that regard.

Synthesis and Reactivity of a Dialane-Bridged Diradical.

Radicals of the lightest group 13 element, boron, are well established and observed in numerous forms. In contrast to boron, radical chemistry involving the heavier group 13 elements (aluminum, gallium, indium, and thallium) remains largely underexplored, primarily attributed to the formidable synthetic challenges associated with these elements. Herein, we report the synthesis and isolation of planar and twisted conformers of a doubly CAAC (cyclic alkyl(amino)carbene)-radical-substituted dialane. Extensive characterization through spectroscopic analyses and X-ray crystallography confirms their identity, while quantum chemical calculations support their open-shell nature and provide further insights into their electronic structures. The dialane-connected diradicals exhibit high susceptibility to oxidation, as evidenced by electrochemical measurements and reactions with o-chloranil and a variety of organic azides. This study opens a previously uncharted class of dialuminum systems to study, broadening the scope of diradical chemistry and its potential applications.

Cu4S Cluster in "0-Hole" and "1-Hole" States: Geometric and Electronic Structure Variations for the Active CuZ* Site of N2O Reductase.

The active site of nitrous oxide reductase (N2OR), a key enzyme in denitrification, features a unique µ4-sulfido-bridged tetranuclear Cu cluster (the so-called CuZ or CuZ* site). Details of the catalytic mechanism have remained under debate and, to date, synthetic model complexes of the CuZ*/CuZ sites are extremely rare due to the difficulty in building the unique {Cu4(µ4-S)} core structure. Herein, we report the synthesis and characterization of [Cu4(µ4-S)]n+ (n = 2, 2; n = 3, 3) clusters, supported by a macrocyclic {py2NHC4} ligand (py = pyridine, NHC = N-heterocyclic carbene), in both their 0-hole (2) and 1-hole (3) states, thus mimicking the two active states of the CuZ* site during enzymatic N2O reduction. Structural and electronic properties of these {Cu4(µ4-S)} clusters are elucidated by employing multiple methods, including X-ray diffraction (XRD), nuclear magnetic resonance (NMR), UV/vis, electron paramagnetic resonance (EPR), Cu/S K-edge X-ray emission spectroscopy (XES), and Cu K-edge X-ray absorption spectroscopy (XAS) in combination with time-dependent density functional theory (TD-DFT) calculations. A significant geometry change of the {Cu4(µ4-S)} core occurs upon oxidation from 2 (τ4(S) = 0.46, seesaw) to 3 (τ4(S) = 0.03, square planar), which has not been observed so far for the biological CuZ(*) site and is unprecedented for known model complexes. The single electron of the 1-hole species 3 is predominantly delocalized over two opposite Cu ions via the central S atom, mediated by a π/π superexchange pathway. Cu K-edge XAS and Cu/S K-edge XES corroborate a mixed Cu/S-based oxidation event in which the lowest unoccupied molecular orbital (LUMO) has a significant S-character. Furthermore, preliminary reactivity studies evidence a nucleophilic character of the central µ4-S in the fully reduced 0-hole state.

Chemical Synthesis of Alpha-Synuclein Proteins via Solid-Phase Peptide Synthesis and Native Chemical Ligation.

Alpha-Synuclein (α-Synuclein) is a 140 amino acid protein implicated in neurodegenerative disorders known as synucleinopathies, where it accumulates in proteinaceous inclusions in the brain. The normal physiological function of α-Synuclein remains obscure, as it exists in several non-neuronal cells in which its function has not been studied. Given the tremendous interest in studying α-Synuclein, and the existing limitations in the production of modified forms of the protein, we developed a method for the chemical synthesis of α-Synuclein by combining peptide fragment synthesis via automated microwave-assisted solid-phase peptide synthesis and ligation strategies. Our synthetic pathway enables the synthesis of protein variants of interest, carrying either mutations or posttranslational modifications, for further investigations of the effects on the structure and aggregation behavior of the protein. Ultimately, our study forms the foundation for future syntheses and studies of other custom-made α-Synuclein variants with a single or several modifications, as necessary.

Ligand Modulation of the Structures and Magnetic Relaxation in Triangular Dy3 Complexes Based on a Tricompartmental Scaffold.

Using a novel tricompartmental hydrazone ligand, a set of trinuclear Dy3 complexes has been isolated and structurally characterized. Complexes Dy3 ⋅ Cl, Dy3 ⋅ Br, and Dy3 ⋅ ClO4 feature a similar overall topology but different anions (Cl- , Br- , or ClO4 - ) in combination with exogenous OH- and solvent co-ligands, which is found to translate into very different magnetic properties. Complex Dy3 ⋅ Cl shows a double relaxation process with fast quantum tunneling of the magnetization, probably related to the structural disorder of µ2 -OH- and µ2 -Cl- co-ligands. Relaxation of the magnetization is slowed down for Dy3 ⋅ Br and Dy3 ⋅ ClO4 , which do not show any structural disorder. In particular, fast quantum tunneling is suppressed in case of Dy3 ⋅ ClO4 , resulting in an energy barrier of 341 K and magnetic hysteresis up to 3.5 K; this makes Dy3 ⋅ ClO4 one of the most robust air-stable trinuclear SMMs. Magneto-structural relationships of the three complexes are analyzed and rationalized with the help of CASSCF/RASSI-SO calculations.

Tuning Magnetic Anisotropy in Co(II) Tetrahedral Carbazole-Modified Phosphine Oxide Single-Ion Magnets: Importance of Structural Distortion versus Heavy-Ion Effect.

Three mononuclear cobalt(II) tetrahedral complexes [Co(CzPh2PO)2X2] (CzPh2PO = (9H-carbazol-9-yl)diphenylphosphine oxide and X = Cl (1), Br (2), I (3)) have been synthesized using a simple synthetic approach to examine their single-ion magnetic (SIM) behavior. A detailed study of the variation in the dynamic magnetic properties of the Co(II) ion in a tetrahedral ligand field has been carried out by the change of the halide ligand. The axial zero-field splitting parameter D was found to vary from -16.4 cm-1 in 1 to -13.8 cm-1 in 2 and +14.6 cm-1 in 3. All the new complexes exhibit field-induced SIM behavior. The results obtained from ab initio CASSF calculations match well with the experimental data, revealing how halide ions induce a change in the D value as we move from Cl- to I-. The ab initio calculations further reveal that the change in the sign of D is due to the multideterminant characteristics of the ground state wave function of 1 and 2, while single-determinant characteristics are instead observed for 3. To gain a better understanding of the relationship between the structural distortion and the sign and magnitude of D values, magnetostructural D correlations were developed using angular relationships, revealing the importance of structural distortions over the heavy halide effect in controlling the sign of D values. This study broadens the scope of employing electronically and sterically modified phosphine oxide ligands in building new types of air-stable Co(II) SIMs.

On the Single-Molecule Magnetic Behavior of Linear Iron(I) Arylsilylamides.

The rational design of 3d-metal-based single-molecule magnets (SMM) requires a fundamental understanding of their intrinsic electronic and structural properties and how they translate into experimentally observable features. Here, we determined the magnetic properties of the linear iron(I) silylamides K{crypt}[FeL2] and [KFeL2] (L = -N(Dipp)SiMe3; crypt = 4,7,13,16,21,24-Hexaoxa-1,10-diazabicyclo[8.8.8]hexacosan). For the former, slow-relaxation of the magnetization with a spin reversal barrier of Ueff = 152 cm-1 as well as a closed-waist magnetic hysteresis and magnetic blocking below 2.5 K are observed. For the more linear [KFeL2], in which the potassium cation is encapsulated by the aryl substituents of the amide ligands, the relaxation barrier and the blocking temperature increase to Ueff = 184 cm-1 and TB = 4.5 K, respectively. The increase is rationalized by a more pronounced axial anisotropy in [KFeL2] determined by dc-SQUID magnetometry. The effective relaxation barrier of [KFeL2] is in agreement with the energy spacing between the ground and first-excited magnetic states, as obtained by field-dependent IR-spectroscopy (178 cm-1), magnetic measurements (208 cm-1), as well as theoretical analysis (212 cm-1). In comparison with the literature, the results show that magnetic coercivity in linear iron(I) silylamides is driven by the degree of linearity in conjunction with steric encumbrance, whereas the ligand symmetry is a marginal factor.

Nonheme FeIV═O Complexes Supported by Four Pentadentate Ligands: Reactivity toward H- and O- Atom Transfer Processes.

Four new pentadentate N5-donor ligands, [N-(1-methyl-2-imidazolyl)methyl-N-(2-pyridyl)-methyl-N-(bis-2-pyridylmethyl)-amine] (L1), [N-bis(1-methyl-2-imidazolyl)methyl-N-(bis-2-pyridylmethyl)amine] (L2), (N-(isoquinolin-3-ylmethyl)-1,1-di(pyridin-2-yl)-N-(pyridin-2-ylmethyl)methanamine (L3), and N,N-bis(isoquinolin-3-ylmethyl)-1,1-di(pyridin-2-yl)methanamine (L4), have been synthesized based on the N4Py ligand framework, where one or two pyridyl arms of the N4Py parent are replaced by (N-methyl)imidazolyl or N-(isoquinolin-3-ylmethyl) moieties. Using these four pentadentate ligands, the mononuclear complexes [FeII(CH3CN)(L1)]2+ (1a), [FeII(CH3CN)(L2)]2+ (2a), [FeII(CH3CN)(L3)]2+ (3a), and [FeII(CH3CN)(L4)]2+ (4a) have been synthesized and characterized. The half-wave potentials (E1/2) of the complexes become more positive in the order: 2a < 1a < 4a ≤ 3a ≤ [Fe(N4Py)(CH3CN)]2+. The order of redox potentials correlates well with the Fe-Namine distances observed by crystallography, which are 2a > 1a ≥ 4a > 3a ≥ [Fe(N4Py)(CH3CN)]2+. The corresponding ferryl complexes [FeIV(O)(L1)]2+ (1b), [FeIV(O)(L2)]2+ (2b), [FeIV(O)(L3)]2+ (3b), and [FeIV(O)(L4)]2+ (4b) were prepared by the reaction of the ferrous complexes with isopropyl 2-iodoxybenzoate (IBX ester) in acetonitrile. The greenish complexes 3b and 4b were also isolated in the solid state by the reaction of the ferrous complexes in CH3CN with ceric ammonium nitrate in water. Mössbauer spectroscopy and magnetic measurements (using superconducting quantum interference device) show that the four complexes 1b, 2b, 3b, and 4b are low-spin (S = 1) FeIV═O complexes. UV/vis spectra of the four FeIV═O complexes in acetonitrile show typical long-wavelength absorptions of around 700 nm, which are expected for FeIV═O complexes with N4Py-type ligands. The wavelengths of these absorptions decrease in the following order: 721 nm (2b) > 706 nm (1b) > 696 nm (4b) > 695 nm (3b) = 695 nm ([FeIV(O) (N4Py)]2+), indicating that the replacement of the pyridyl arms with (N-methyl) imidazolyl moieties makes L1 and L2 exert weaker ligand fields than the parent N4Py ligand, while the ligand field strengths of L3 and L4 are similar to the N4Py parent despite the replacement of the pyridyl arms with N-(isoquinolin-3-ylmethyl) moieties. Consequently, complexes 1b and 2b tend to be less stable than the parent [FeIV(O)(N4Py)]2+ complex: the half-life sequence at room temperature is 1.67 h (2b) < 16 h (1b) < 45 h (4b) < 63 h (3b) ≈ 60 h ([FeIV(O)(N4Py)]2+). Compared to the parent complex, 1b and 2b exhibit enhanced reactivity in both the oxidation of thioanisole in the oxygen atom transfer (OAT) reaction and the oxygenation of C-H bonds of aromatic and aliphatic substrates, presumed to occur via an oxygen rebound process. Furthermore, the second-order rate constants for hydrogen atom transfer (HAT) reactions affected by the ferryl complexes can be directly related to the C-H bond dissociation energies of a range of substrates that have been studied. Using either IBX ester or H2O2 as an oxidant, all four new FeII complexes display good performance in catalytic reactions involving both HAT and OAT reactions.

Fully Delocalized Mixed-Valent Cu1.5 Cu1.5 Complex: Strong Cu-Cu interaction and Fast Electron Self-Exchange Rate Despite Large Structural Changes.

A flexible macrocyclic ligand with two tridentate {CNC} compartments can host two Cu ions in reversibly interconvertible states, CuI CuI (1) and mixed-valent Cu1.5 Cu1.5 (2). They were characterized by XRD and multiple spectroscopic methods, including EPR, UV/Vis absorption and MCD, in combination with TD-DFT and CASSCF calculations. 2 features a short Cu⋅⋅⋅Cu distance (≈2.5 Å; compared to ≈4.0 Šin 1) and a very high delocalization energy of 13 000 cm-1 , comparable to the mixed-valent state of the biological CuA site. Electron self-exchange between 1 and 2 is rapid despite large structural reorganization, and is proposed to proceed via a sequential mechanism involving an active conformer of 1, viz. 1'; the latter has been characterized by XRD. Such electron transfer (ET) process is reminiscent of the conformationally gated ET proposed for biological systems. This redox couple is a unique pair of flexible dicopper complexes, achieving fast electron self-exchange closely related to the function of the CuA site.

Combining Valence-to-Core X-ray Emission and Cu K-edge X-ray Absorption Spectroscopies to Experimentally Assess Oxidation State in Organometallic Cu(I)/(II)/(III) Complexes.

A series of organometallic copper complexes in formal oxidation states ranging from +1 to +3 have been characterized by a combination of Cu K-edge X-ray absorption (XAS) and Cu Kß valence-to-core X-ray emission spectroscopies (VtC XES). Each formal oxidation state exhibits distinctly different XAS and VtC XES transition energies due to the differences in the Cu Zeff, concomitant with changes in physical oxidation state from +1 to +2 to +3. Herein, we demonstrate the sensitivity of XAS and VtC XES to the physical oxidation states of a series of N-heterocyclic carbene (NHC) ligated organocopper complexes. We then extend these methods to the study of the [Cu(CF3)4]- ion. Complemented by computational methods, the observed spectral transitions are correlated with the electronic structure of the complexes and the Cu Zeff. These calculations demonstrate that a contraction of the Cu 1s orbitals to deeper binding energy upon oxidation of the Cu center manifests spectroscopically as a stepped increase in the energy of both XAS and Kß2,5 emission features with increasing formal oxidation state within the [Cun+(NHC2)]n+ series. The newly synthesized Cu(III) cation [CuIII(NHC4)]3+ exhibits spectroscopic features and an electronic structure remarkably similar to [Cu(CF3)4]-, supporting a physical oxidation state assignment of low-spin d8 Cu(III) for [Cu(CF3)4]-. Combining XAS and VtC XES further demonstrates the necessity of combining multiple spectroscopies when investigating the electronic structures of highly covalent copper complexes, providing a template for future investigations into both synthetic and biological metal centers.

Polynuclear Iron(II) Pyridonates: Synthesis and Reactivity of Fe4 and Fe5 Clusters.

The combination of pyridonate ligands with transition metal ions enables the synthesis of an especially rich set of diverse coordination compounds involving various κ- and µ-bonding modes and higher nuclearities. With iron(II) ions, this chemical space is rather poorly explored beyond some biomimetic models of the pyridone iron-containing hydrogenase. Here, the topologically new Fe5 and Fe4 clusters, Fe5(LH)6[N(SiMe3)2]4 (1) and Fe4(LMe)6[N(SiMe3)2]2 (2), were synthesized (LH = 2-pyridonate; LMe = 6-methyl-2-pyridonate). Complex 1 contained an unprecedented diamondoid Fe@Fe4 tetrahedron with a central-to-peripheral Fe-Fe distance of ∼3.1 Å. The crystal structure of complex 2 displayed an Fe4O6 butterfly motif containing a planar Fe4 arrangement. Mössbauer spectroscopy confirmed the high-spin ferrous character of all iron ions. SQUID magnetometry reveals that the Fe(II) ions are involved in weak magnetic exchange coupling across the pyridonate bridges that results in antiferromagnetic interactions. The Fe4 cluster exhibits slow relaxation of magnetization under an applied magnetic field with an effective energy barrier of 38.5 K, rarely observed among the very rare examples of Fe(II) cluster-based single-molecule magnets. Studies of protolytic substitution of the amido ligands demonstrated the lability of the diamondoid Fe5 core in 1 and the stability of the Fe4 rhomboid in 2.

Organometallic µ-Nitridodiiron Complexes in Oxidation States Ranging from (III/III) to (IV/IV).

Iron complexes with nitrido ligands are of interest as molecular analogues of key intermediates during N2-to-NH3 conversion in industrial or enzymatic processes. Dinuclear iron complexes with a bridging nitrido unit are mostly known in relatively high oxidation states (III/IV or IV/IV), originating from the decomposition of azidoiron precursors via high-valent Fe≡N intermediates. The use of a tetra-NHC macrocyclic scaffold ligand (NHC = N-heterocyclic carbene) has now allowed for the isolation of a series of organometallic µ-nitridodiiron complexes ranging from the mid-valent FeIII-N-FeIII (1) via mixed-valent FeIII-N-FeIV (type 4) to the high-valent FeIV-N-FeIV (type 5) species that are interconverted at moderate potentials, accompanied by axial ligand binding at the FeIV sites. Magnetic measurements and electron paramagnetic resonance spectroscopy showed the homovalent complexes to be diamagnetic and the mixed-valent system to feature an S = 1/2 ground state due to very strong antiferromagnetic coupling. The bonding in the Fe-N-Fe moiety has been further probed by crystallographic structure determination, 57Fe Mössbauer and UV-vis spectroscopies, as well as density functional theory computations, which revealed high covalency and nearly identical Fe-N distances across this redox series. The latter has been rationalized in terms of the nonbonding nature of the combination of Fe dz2 atomic orbitals from which electrons are successively removed upon oxidation, and these redox processes are best described as being metal-centered. The tetra-NHC-ligated µ-nitridodiiron series complements a set of related complexes with single-atom µ-oxido and µ-phosphido bridges, but the Fe-N-Fe core exhibits a comparatively high stability over several oxidation states. This promises interesting applications in view of the manifold catalytic uses of µ-nitridodiiron complexes based on macrocyclic N-donor porphinato(2-) or phthalocyaninato(2-) ligands.

Borylation in the Second Coordination Sphere of FeII Cyanido Complexes and Its Impact on Their Electronic Structures and Excited-State Dynamics.

Second coordination sphere interactions of cyanido complexes with hydrogen-bonding solvents and Lewis acids are known to influence their electronic structures, whereby the non-labile attachment of B(C6F5)3 resulted in several particularly interesting new compounds lately. Here, we investigate the effects of borylation on the properties of two FeII cyanido complexes in a systematic manner by comparing five different compounds and using a range of experimental techniques. Electrochemical measurements indicate that borylation entails a stabilization of the FeII-based t2g-like orbitals by up to 1.65 eV, and this finding was confirmed by Mössbauer spectroscopy. This change in the electronic structure has a profound impact on the UV-vis absorption properties of the borylated complexes compared to the non-borylated ones, shifting their metal-to-ligand charge transfer (MLCT) absorption bands over a wide range. Ultrafast UV-vis transient absorption spectroscopy provides insight into how borylation affects the excited-state dynamics. The lowest metal-centered (MC) excited states become shorter-lived in the borylated complexes compared to their cyanido analogues by a factor of ∼10, possibly due to changes in outer-sphere reorganization energies associated with their decay to the electronic ground state as a result of B(C6F5)3 attachment at the cyanido N lone pair.