An in-depth study of the mechanism of the azidation of C(sp³)-H bonds with Zhdankin's λ³-azidoiodane reagent catalyzed by iron(II)(pybox) complexes is reported. Previously, it was shown that tertiary and benzylic C(sp³)-H bonds of a range of complex molecules underwent highly site-selective azidation by reaction with a λ³-azidoiodane reagent and an iron(II)(pybox) catalyst under mild conditions. However, the mechanism of this reaction was unclear. Here, a series of mechanistic experiments are presented that reveal critical features responsible for the high selectivity and broad scope of this reaction. These experiments demonstrate the ability of the λ³-azidoiodane reagent to undergo I-N bond homolysis under mild conditions to form λ²-iodanyl and azidyl radicals that undergo highly site-selective and rate-limiting abstraction of a hydrogen atom from the substrate. The resultant alkyl radical then combines rapidly with a resting state iron(III)-azide complex, which is generated by the reaction of the λ³-azidoiodane with the iron(II)(pybox) complex, to form the C(sp³)-N₃ bond. This mechanism is supported by the independent synthesis of well-defined iron complexes characterized by cyclic voltammetry, X-ray diffraction, and EPR spectroscopy, and by the reaction of the iron complexes with alkanes and the λ³-azidoiodane. Reaction monitoring and kinetic studies further reveal an unusual effect of the catalyst on the rate of formation of product and consumption of reactants and suggest a blueprint for the development of new processes leading to late-stage functionalization of C(sp³)-H bonds.

The primary electron donor P₇₀₀ of the photosystem I (PSI) is a heterodimer consisting of two chlorophyll molecules. A series of electron-transfer events immediately following the initial light excitation leads to a stabilization of the positive charge by its cation radical form, P₇₀₀^+•. The electronic structure of P₇₀₀^+• and, in particular, its asymmetry with respect to the two chlorophyll monomers is of fundamental interest and is not fully understood up to this date. Here, we apply multifrequency X- (9 GHz) and Q-band (35 GHz) hyperfine sublevel correlation (HYSCORE) spectroscopy to investigate the electron spin density distribution in the cation radical P₇₀₀^+• of PSI from a thermophilic cyanobacterium Thermosynechococcus elongatus. Six ¹⁴N and two ¹H distinct nuclei have been resolved in the HYSCORE spectra and parameters of the corresponding nuclear hyperfine and quadrupolar hyperfine interactions were obtained by combining the analysis of HYSCORE spectral features with direct numerical simulations. Based on a close similarity of the nuclear quadrupole tensor parameters, all of the resolved ¹⁴N nuclei were assigned to six out of total eight available pyrrole ring nitrogen atoms (i.e., four in each of the chlorophylls), providing direct evidence of spin density delocalization over the both monomers in the heterodimer. Using the obtained experimental values of the ¹⁴N electron-nuclear hyperfine interaction parameters, the upper limit of the electron spin density asymmetry parameter is estimated as R_A/B^upper = 7.7 ± 0.5, while a tentative assignment of ¹⁴N observed in the HYSCORE spectra yields R_B/A = 3.1 ± 0.5.

Analysis of the electronic structure and local coordination of an element is an important aspect in the study of the chemical and physical properties of materials. This is particularly relevant at the nanoscale where new phases of matter may emerge below a critical size. X-ray emission spectroscopy (XES) at synchrotron radiation sources and free electron lasers has enriched the field of X-ray spectroscopy. The spectroscopic techniques derived from the combination of X-ray absorption and emission spectroscopy (XAS-XES), such as resonant inelastic X-ray scattering (RIXS) and high energy resolution fluorescence detected (HERFD) XAS, are an ideal tool for the study of nanomaterials. New installations and beamline upgrades now often include wavelength dispersive instruments for the analysis of the emitted X-rays. With the growing use of XAS-XES, scientists are learning about the possibilities and pitfalls. We discuss some experimental aspects, assess the feasibility of measuring weak fluorescence lines in dilute, radiation sensitive samples, and present new experimental approaches for studying magnetic properties of colloidal nanoparticles directly in the liquid phase.

We report the synthesis, characterization, and reactivity of [LFe₃ (PhPz)₃ OMn(^s PhIO)][OTf]_x (3: x=2; 4: x=3), where 4 is one of very few examples of iodosobenzene-metal adducts characterized by X-ray crystallography. Access to these rare heterometallic clusters enabled differentiation of the metal centers involved in oxygen atom transfer (Mn) or redox modulation (Fe). Specifically, ⁵⁷ Fe Mössbauer and X-ray absorption spectroscopy provided unique insights into how changes in oxidation state (Fe^III₂ Fe^II Mn^II vs. Fe^III₃ Mn^II ) influence oxygen atom transfer in tetranuclear Fe₃ Mn clusters. In particular, a one-electron redox change at a distal metal site leads to a change in oxygen atom transfer reactivity by ca. two orders of magnitude.

Spin-vibronic coupling leads to spin relaxation in paramagnetic molecules, and an understanding of factors that contribute to this phenomenon is essential for designing next-generation spintronics technology, including single-molecule magnets and spin-based qubits, wherein long-lifetime magnetic ground states are desired. We report spectroscopic and magnetic characterization of the isoelectronic and isostructural series of homoleptic zerovalent transition metal triad M(CNDipp)₆ (M = V, Nb, Ta; CNDipp = 2,6-diisopropylphenyl isocyanide) and show experimentally the significant increase in spin relaxation rate upon going from V to Nb to Ta. Correlated electronic calculations and first principle spin-phonon computations support the role of spin-orbit coupling in modulating spin-phonon relaxation. Our results provide experimental evidence that increasing magnetic anisotropy through spin-orbit coupling interactions leads to increased spin-vibronic relaxation, which is detrimental to long spin lifetime in paramagnetic molecules.

In photosynthesis, photosystem II (PSII) is the multi-subunit membrane protein complex that catalyzes photo-oxidation of water into dioxygen through the oxygen evolving complex (OEC). To understand the water oxidation reaction, it is important to get structural information about the transient and intermediate states of the OEC in the dimeric PSII core complex (dPSIIcc). In recent times, femtosecond X-ray pulses from the free electron laser (XFEL) are being used to obtain X-ray diffraction (XRD) data of dPSIIcc microcrystals at room temperature that are free of radiation damage. In our experiments at the XFEL, we used an electrospun liquid microjet setup that requires microcrystals less than 40 μm in size. In this study, we explored various microseeding techniques to get a high yield of monodisperse uniform-sized microcrystals. Monodisperse microcrystals of dPSIIcc of uniform size were a key to improve the stability of the jet and the quality of XRD data obtained at the XFEL. This was evident by an improvement of the quality of the datasets obtained, from 6.5Å, using crystals grown without the micro seeding approach, to 4.5Å using crystals generated with the new method.

In plants, algae and cyanobacteria, Photosystem II (PSII) catalyzes the light-driven splitting of water at a protein-bound Mn₄CaO₅-cluster, the water-oxidizing complex (WOC). In the photosynthetic organisms, the light-driven formation of the WOC from dissolved metal ions is a key process because it is essential in both initial activation and continuous repair of PSII. Structural information is required for understanding of this chaperone-free metal-cluster assembly. For the first time, we obtained a structure of PSII from Thermosynechococcus elongatus without the Mn₄CaO₅-cluster. Surprisingly, cluster-removal leaves the positions of all coordinating amino acid residues and most nearby water molecules largely unaffected, resulting in a pre-organized ligand shell for kinetically competent and error-free photo-assembly of the Mn₄CaO₅-cluster. First experiments initiating (i) partial disassembly and (ii) partial re-assembly after complete depletion of the Mn₄CaO₅-cluster agree with a specific bi-manganese cluster, likely a di-µ-oxo bridged pair of Mn(III) ions, as an assembly intermediate.

The S₃ state is currently the last observable intermediate prior to O-O bond formation at the oxygen-evolving complex (OEC) of Photosystem II, and its electronic structure has been assigned to a homovalent Mn^IV₄ core with an S = 3 ground state. While structural interpretations based on the EPR spectroscopic features of the S₃ state provide valuable mechanistic insight, corresponding synthetic and spectroscopic studies on tetranuclear complexes mirroring the Mn oxidation states of the S₃ state remain rare. Herein, we report the synthesis and characterization by XAS and multifrequency EPR spectroscopy of a Mn^IV₄O₄ cuboidal complex as a spectroscopic model of the S₃ state. Results show that this Mn^IV₄O₄ complex has an S = 3 ground state with isotropic ⁵⁵Mn hyperfine coupling constants of -75, -88, -91, and 66 MHz. These parameters are consistent with an αααβ spin topology approaching the trimer-monomer magnetic coupling model of pseudo-octahedral Mn^IV centers. Importantly, the spin ground state changes from S = 1/2 to S = 3 as the OEC is oxidized from the S₂ state to the S₃ state. This same spin state change is observed following oxidation of the previously reported Mn^IIIMn^IV₃O₄ cuboidal complex to the Mn^IV₄O₄ complex described here. This sets a synthetic precedent for the observed low-spin to high-spin conversion in the OEC.

Despite extensive biochemical, spectroscopic, and computational studies, the mechanism of biological water oxidation by the oxygen evolving complex (OEC) of Photosystem II remains a subject of significant debate. Mechanistic proposals are guided by the characterization of reaction intermediates such as the S₂ state, which features two characteristic EPR signals at g = 2 and g = 4.1. Two nearly isoenergetic structural isomers have been proposed as the source of these distinct signals, but relevant structure-electronic structure studies remain rare. Herein, we report the synthesis, crystal structure, electrochemistry, XAS, magnetic susceptibility, variable temperature CW-EPR, and pulse EPR data for a series of [Mn^IIIMn₃^IVO₄] cuboidal complexes as spectroscopic models of the S₂ state of the OEC. Resembling the oxidation state and EPR spectra of the S₂ state of the OEC, these model complexes show two EPR signals, a broad low field signal and a multiline signal, that are remarkably similar to the biological system. The effect of systematic changes in the nature of the bridging ligands on spectroscopy were studied. Results show that the electronic structure of tetranuclear Mn complexes is highly sensitive to even small geometric changes and the nature of the bridging ligands. Our model studies suggest that the spectroscopic properties of the OEC may also react very sensitively to small changes in structure; the effect of protonation state and other reorganization processes need to be carefully assessed.