Spin-Lattice Relaxation and Spin-Phonon Coupling of s Metal Ions at the Surface.

To use transition metal ions for spin-based applications, it is essential to understand fundamental contributions to electron spin relaxation in different ligand environments. For example, to serve as building blocks for a device, transition metal ion-based molecular qubits must be organized on surfaces and preserve long electron spin relaxation times, up to room temperature. Here we propose monovalent group 12 ions (Zn and Cd) as potential electronic metal qubits with an s ground state.

Short-Range Electronic Interactions between Vanadium and Molybdenum in Bimetallic SAPO-5 Catalysts Revealed by Hyperfine Spectroscopy.

Engineering two cooperative sites into a catalyst implies the onset of synergistic effects related to the existence of short-range electronic interactions between two metal components. However, these interactions and the relative structure-property correlations are often difficult to obtain. Here we show that hyperfine spectroscopy has the potential to reveal the presence of V-O-Mo linkages assessing the degree of spin density transfer from paramagnetic V species to proximal oxo-bridged Mo metal ions.

Unveiling the atomistic and electronic structure of Ni-NO adduct in a MOF-based catalyst by EPR spectroscopy and quantum chemical modelling.

The nature of the chemical bonding between NO and open-shell Ni ions docked in a metal-organic framework is fully characterized by EPR spectroscopy and computational methods. High-frequency EPR experiments reveal the presence of unsaturated Ni ions displaying five-fold coordination. Upon NO adsorption, in conjunction with advanced EPR methodologies and DFT/CASSCF modelling, the covalency of the metal-NO and metal-framework bonds is directly quantified.

Single Metal Atoms on Oxide Surfaces: Assessing the Chemical Bond through O Electron Paramagnetic Resonance.

ConspectusEven in the gas phase single atoms possess catalytic properties, which can be crucially enhanced and modulated by the chemical interaction with a solid support. This effect, known as electronic metal-support interaction, encompasses charge transfer, orbital overlap, coordination structure, etc., in other words, all the crucial features of the chemical bond.

The Structure of Monomeric Hydroxo-Cu Species in Cu-CHA. A Quantitative Assessment.

Using EPR and HYSCORE spectroscopies in conjunction with calculations, we assess the structure of framework-bound monomeric hydroxo-Cu in copper-loaded chabazite (CHA). The species is an interfacial distorted square-planar [CuOH(O-8MRs)] complex located at eight-membered-ring windows, displaying three coordinating bonds with zeolite lattice oxygens and the hydroxo ligand hydrogen-bonded to the cage. The complex has a distinctive EPR signature with = [2.

O-EPR determination of the structure and dynamics of copper single-metal sites in zeolites.

The bonding of copper ions to lattice oxygens dictates the activity and selectivity of copper exchanged zeolites. By O isotopic labelling of the zeolite framework, in conjunction with advanced EPR methodologies and DFT modelling, we determine the local structure of single site Cu species, we quantify the covalency of the metal-framework bond and we assess how this scenario is modified by the presence of solvating HO or HO molecules. This enables to follow the migration of Cu species as a function of hydration conditions, providing evidence for a reversible transfer pathway within the zeolite cage as a function of the water pressure.

Electrochemical CO reduction in water at carbon cloth electrodes functionalized with a fac-Mn(apbpy)(CO)Br complex.

The organometallic complex (fac-Mn(apbpy)(CO)3Br) (apbpy = 4-(4-aminophenyl)-2,2'-bipyridine) grafted electrochemically onto carbon cloth serves as an electrocatalyst in the aqueous reduction of CO2 to syngas. A faradaic efficiency of around 60% for CO and 40% for H2 at -1.35 V is achieved together with a productivity rate higher than 870 NlCO h-1 gMn-1 at turnover numbers of up to 33 200 during 10 hours of operation.

Interfacing CRYSTAL/AMBER to Optimize QM/MM Lennard⁻Jones Parameters for Water and to Study Solvation of TiO₂ Nanoparticles.

Metal oxide nanoparticles (NPs) are regarded as good candidates for many technological applications, where their functional environment is often an aqueous solution. The correct description of metal oxide electronic structure is still a challenge for local and semilocal density functionals, whereas hybrid functional methods provide an improved description, and local atomic function-based codes such as CRYSTAL17 outperform plane wave codes when it comes to hybrid functional calculations. However, the computational cost of hybrids are still prohibitive for systems of real sizes, in a real environment.

Assessment of Density Functional Approximations for Highly Correlated Oxides: The Case of CeO and CeO.

CeO based materials are very attractive as catalytic components for industrial processes and environmentally friendly technologies; therefore, a reliable and computationally affordable theoretical description of the main properties of ceria is needed. In particular, the description of the interconversion between the Ce(IV) and Ce(III) oxidation states, on which lies the main chemical features of the cerium oxide, results in quite a challenge at the Density Functional Theory level. Here, we tested several density functional approximations, spanning from GGA to hybrid (Global, Meta-Global, and Range Separated Corrected) functionals, on the structural, vibrational, electronic, and thermochemical properties of bulk CeO and CeO.

Electrochemical CO Reduction at Glassy Carbon Electrodes Functionalized by Mn and Re Organometallic Complexes.

The catalytic activities towards electrochemical CO reduction of two new rhenium and manganese complexes, namely fac-Mn(apbpy)(CO) Br (1) and fac-Re(apbpy)(CO) Cl (2) (apbpy=4-(4-aminophenyl)-2,2'-bipyridine), in both homogeneous and heterogeneous phases are compared. A glassy carbon electrode (GCE) surface has been functionalized with complexes 1 and 2 by two approaches: a) direct electrochemical oxidation of the amino group with formation of C-N bonds, and b) electrochemical reduction of the corresponding diazonium salts with formation of C-C bonds. The chemically modified GCEs show efficient conversion of CO into CO, with turnover numbers (TONs) about 60 times higher than those of the corresponding catalysts in homogeneous solutions, and in a much shorter time.

Mass spectrometric fragmentation and photocatalytic transformation of nicotine and cotinine.

Rationale: Nicotine and cotinine are, respectively, alkaloids produced mainly by the Solanaceae plant family, especially tobacco, and its most important human metabolite. These compounds are frequently found as contaminants in wastewater or landfill samples and they could be used to evaluate pollution by tobacco use. The aim of this study is to improve the knowledge about possible transformation pathways of nicotine and cotinine.

Upconverting Nanoparticles Prompt Remote Near-Infrared Photoactivation of Ru(II)-Arene Complexes.

The synthesis and full characterisation (including X-ray diffraction studies and DFT calculations) of two new piano-stool Ru(II) -arene complexes, namely [(η(6) -p-cym)Ru(bpy)(m-CCH-Py)][(PF)6]2 (1) and [(η(6) -p-cym)Ru(bpm)(m-CCH-Py)][(PF)6]2 (2; p-cym=p-cymene, bpy=2,2'-bipyridine, bpm=2,2'-bipyrimidine, and m-CCH-Py=3-ethynylpyridine), is described and discussed. The reaction of the m-CCH-Py ligand of 1 and 2 with diethyl-3-azidopropyl phosphonate by Cu-catalysed click chemistry affords [(η(6) -p-cym)Ru(bpy)(P-Trz-Py)][(PF)6]2 (3) and [(η(6) -p-cym)Ru(bpm)(P-Trz-Py)][(PF)6]2 (4; P-Trz-Py=[3-(1-pyridin-3-yl-[1,2,3]triazol-4-yl)-propyl]phosphonic acid diethyl ester). Upon light excitation at λ=395 nm, complexes 1-4 photodissociate the monodentate pyridyl ligand and form the aqua adduct ions [(η(6) -p-cym)Ru(bpy)(H2O)](2+) and [(η(6) -p-cym)Ru(bpm)(H2O)](2+).

Photorelease of Pyridyl Esters in Organometallic Ru(II) Arene Complexes.

New Ru(II) arene complexes of formula [(η6-p-cym)Ru(N-N)(X)]2+ (where p-cym = para-cymene, N-N = 2,2'-bipyrimidine (bpm) or 2,2'-bipyridine (bpy) and X = m/p-COOMe-Py, 1-4) were synthesised and characterized, including the molecular structure of complexes [(η6-p-cym)Ru(bpy)(m-COOMe-Py)]2+ (3) and [(η6-p-cym)Ru(bpy) (p-COOMe-Py)]2+ (4) by single-crystal X-ray diffraction. Complexes 1-4 are stable in the dark in aqueous solution over 48 h and photolysis studies indicate that they can photodissociate the monodentate m/p-COOMe-Py ligands selectively with yields lower than 1%. DFT and TD-DFT calculations (B3LYP/LanL2DZ/6-31G**) performed on singlet and triplet states pinpoint a low-energy triplet state as the reactive state responsible for the selective dissociation of the monodentate pyridyl ligands.

Probing hydrogen bond networks in half-sandwich Ru(II) building blocks by a combined 1H DQ CRAMPS solid-state NMR, XRPD, and DFT approach.

The hydrogen bond network of three polymorphs (1α, 1β, and 1γ) and one solvate form (1·H2O) arising from the hydration-dehydration process of the Ru(II) complex [(p-cymene)Ru(κN-INA)Cl2] (where INA is isonicotinic acid), has been ascertained by means of one-dimensional (1D) and two-dimensional (2D) double quantum (1)H CRAMPS (Combined Rotation and Multiple Pulses Sequences) and (13)C CPMAS solid-state NMR experiments. The resolution improvement provided by homonuclear decoupling pulse sequences, with respect to fast MAS experiments, has been highlighted. The solid-state structure of 1γ has been fully characterized by combining X-ray powder diffraction (XRPD), solid-state NMR, and periodic plane-wave first-principles calculations.

In-vivo degradation of poly(carbonate-urethane) based spine implants.

Fourteen explanted Dynesys® spinal devices were analyzed for biostability and compared with a reference, never implanted, control. Both poly(carbonate-urethane) (PCU) spacers and polyethylene-terephthalate (PET) cords were analyzed. The effect of implantation was evaluated through the observation of physical alterations of the device surfaces, evaluation of the chemical degradation and fluids absorption on the devices and examination of the morphological and mechanical features.

High energy resolution core-level X-ray spectroscopy for electronic and structural characterization of osmium compounds.

A comprehensive study of the bulk solid OsCl3 and the molecular ion [Os(bpy)2(CO)Cl](+) is presented illustrating the application of RIXS and HERFD XANES spectroscopies to the investigation of both bulk materials and molecular complexes. In order to analyze the experimental results, DFT simulations were performed taking into account spin-orbit interaction. Calculations for both compounds resulted in good agreement with the experimental RIXS and HERFD XANES data, shedding light on the details of their local atomic and electronic structure.

Effect of ceria structural properties on the catalytic activity of Au-CeO2 catalysts for WGS reaction.

Two gold based catalysts supported on ceria prepared by different methods (urea gelation coprecipitation, UGC, and coprecipitation, CP) have been synthesized and tested in the WGS reaction, showing quite different catalytic behaviors. Interestingly, the two catalysts have the same gold loading (3 wt% Au was inserted by deposition-precipitation) and the FTIR spectroscopy of the adsorbed CO revealed the same amount of gold exposed sites. With the aim to elucidate how the preparation method affects the properties of the support, a morphological, structural and textural characterization has been performed by HRTEM, XRD, BET and Raman analyses, as well as FTIR spectroscopy to probe both the Au and the support exposed sites.

The photochemistry of transition metal complexes using density functional theory.

The use of density functional theory (DFT) and time-dependent DFT (TD-DFT) to study the photochemistry of metal complexes is becoming increasingly important among chemists. Computational methods provide unique information on the electronic nature of excited states and their atomic structure, integrating spectroscopy observations on transient species and excited-state dynamics. In this contribution, we present an overview on photochemically active transition metal complexes investigated by DFT.

Soft synthesis of isocyanate-functionalised metal-organic frameworks.

We have developed an original synthetic pathway for the conversion of a MIL-68(In)-NH(2) metal-organic framework into its corresponding isocyanate (-NCO) derivative. This two-step soft post-modification technique leads to highly porous isostructural materials.

Resonant X-ray emission spectroscopy reveals d-d ligand-field states involved in the self-assembly of a square-planar platinum complex.

Resonant X-ray Emission Spectroscopy (RXES) is used to characterize the ligand field states of the prototypic self-assembled square-planar complex, [Pt(tpy)Cl]Cl (tpy=2,2':6',2''-terpyridine), and determine the effect of weak metal-metal and π-π interactions on their energy.

HYSCORE and Davies ENDOR study of irradiated ultra high molecular weight polyethylene.

Ultra high molecular weight polyethylene (UHMWPE) has been studied with different magnetic resonance techniques to elicit information on the nature and the location of radicals generated during high energy irradiation. Field swept electron paramagnetic resonance, pulsed Davies electron nuclear double resonance and hyperfine sublevel correlation spectroscopic measurements allowed extracting for the first time the full (1) H hyperfine coupling tensors of the most abundant radical, i.e.

Low temperature activation and reactivity of CO2 over a Cr(II)-based heterogeneous catalyst: a spectroscopic study.

A new heterogeneous catalyst for CO(2) activation was identified in the Cr(II)/SiO(2) Phillips catalyst, one of the most important catalysts used industrially for olefin polymerization. Interestingly, it was found that Cr(II)/SiO(2) strongly activates CO(2) already at room temperature, making it available for chemicals synthesis. A preliminary attempt in this direction was done by following the reaction of CO(2) with ethylene oxide at room temperature by means of FT-IR spectroscopy, which showed the formation of ethylene carbonate.

Ru(x)Pt(y)Sn(z) cluster-derived nanoparticle catalysts: spectroscopic investigation into the nature of active multinuclear single sites.

Cluster-derived Ru(x)Pt(y)Sn(z) nanoparticles are active catalysts in the hydrogenation of nitrobenzene. The nature of the active sites has been elucidated by FTIR spectroscopy using CO and NO as probe molecules. A new metal carbonyl cluster precursor, Pt(2)Ru(2)(SnBu(t)(3))(2)(CO)(9)(μ-H)(2), has been synthesized to obtain a Ru(2)Pt(2)Sn(2)/SiO(2) catalyst, that displayed remarkably high levels of conversion and selectivities compared to other bi-and monometallic analogues.

Tailoring metal-organic frameworks for CO2 capture: the amino effect.

Carbon dioxide capture from processes is one of the strategies adopted to decrease anthropogenic greenhouse gas emissions. To lower the cost associated with the regeneration of amine-based scrubber systems, one of the envisaged strategies is the grafting of amines onto high-surface-area supports and, in particular, onto metal-organic frameworks (MOFs). In this study, the interaction between CO(2) and aliphatic and aromatic amines has been characterized by quantum mechanical methods (MP2), focusing attention both on species already reported in MOFs and on new amine-based linkers, to inspire the rational synthesis of new high-capacity MOFs.