A tetrahedral neptunium(V) complex.

Neptunium is an actinide element sourced from anthropogenic production, and, unlike naturally abundant uranium, its coordination chemistry is not well developed in all accessible oxidation states. High-valent neptunium generally requires stabilization from at least one metal-ligand multiple bond, and departing from this structural motif poses a considerable challenge. Here we report a tetrahedral molecular neptunium(V) complex ([Np5+(NPC)4][B(ArF5)4], 1-Np) (NPC = [NPtBu(pyrr)2]-; tBu = C(CH3)3; pyrr = pyrrolidinyl (N(C2H4)2); B(ArF5)4 = tetrakis(2,3,4,5,6-pentafluourophenyl)borate). Single-crystal X-ray diffraction, solution-state spectroscopy and density functional theory studies of 1-Np and the product of its proton-coupled electron transfer (PCET) reaction, 2-Np, demonstrate the unique bonding that stabilizes this reactive ion and establishes the thermochemical and kinetic parameters of PCET in a condensed-phase transuranic complex. The isolation of this four-coordinate, neptunium(V) complex reveals a fundamental reaction pathway in transuranic chemistry.

What is the nature of the uranium(iii)-arene bond?

Complexes of the form [U(η6-arene)(BH4)3] where arene = C6H6; C6H5Me; C6H3-1,3,5-R3 (R = Et, iPr, tBu, Ph); C6Me6; and triphenylene (C6H4)3 were investigated towards an understanding of the nature of the uranium-arene interaction. Density functional theory (DFT) shows the interaction energy reflects the interplay between higher energy electron rich π-systems which drive electrostatic contributions, and lower energy electron poor π-systems which give rise to larger orbital contributions. The interaction is weak in all cases, which is consistent with the picture that emerges from a topological analysis of the electron density where metrics indicative of covalency show limited dependence on the nature of the ligand - the interaction is predominantly electrostatic in nature. Complete active space natural orbital analyses reveal low occupancy U-arene π-bonding interactions dominate in all cases, while δ-bonding interactions are only found with high-symmetry and electron-rich C6Me6. Finally, both DFT and multireference calculations on a reduced, formally U(ii), congener, [U(C6Me6)(BH4)3]-, suggests the electronic structure (S = 1 or 2), and hence metal oxidation state, of such a species cannot be deduced from structural features such as arene distortion alone. We show that arene geometry strongly depends on the spin-state of the complex, but that in both spin-states the complex is best described as U(iii) with an arene-centred radical.

Molecular Geometry and Electronic Structure of Copper Corroles.

Copper corroles are known for their unique multiconfigurational electronic structures in the ground state, which arise from the transfer of electrons from the π orbitals of the corrole to the d-orbital of copper. While density functional theory (DFT) provides reasonably good molecular geometries, the determination of the ground spin state and the associated energetics is heavily influenced by functional choice, particularly the percentage of the Hartree-Fock exchange. Using extended multireference perturbation theory methods (XMS-CASPT2), the functional choice can be assessed. The molecular geometries and electronic structures of both the unsubstituted and the meso-triphenyl copper corroles were investigated. A minimal active space was employed for structural characterization, while larger active spaces are required to examine the electronic structure. The XMS-CASPT2 investigations conclusively identify the ground electronic state as a multiconfigurational singlet (S0) with three dominant electronic configurations in its lowest energy and characteristic saddled structure. In contrast, the planar geometry corresponds to the triplet state (T0), which is approximately 5 kcal/mol higher in energy compared to the S0 state for both the bare and substituted copper corroles. Notably, the planarity of the T0 geometry is reduced in the substituted corrole compared with that in the unsubstituted one. By analyzing the potential energy surface (PES) between the S0 and T0 geometries using XMS-CASPT2, the multiconfigurational electronic structure is shown to transition toward a single electron configuration as the saddling angle decreases (i.e., as one approaches the planar geometry). Despite the ability of the functionals to reproduce the minimum energy structures, only the TPSSh-D3 PES is reasonably close to the XMS-CASPT2 surface. Significant deviations along the PES are observed with other functionals.

Spin-state energetics and magnetic anisotropy in penta-coordinated Fe(III) complexes with different axial and equatorial ligand environments.

The penta-coordinated trigonal-bi-pyramidal (TBP) Fe(III) complex (PMe2Ph)2FeCl3 shows a reduced magnetic anisotropy in its intermediate-spin (IS) state as compared to its methyl-analog (PMe3)2Fe(III)Cl3. In this work, the ligand environment in (PMe2Ph)2FeCl3 is systematically altered by replacing the axial -P with -N and -As, the equatorial -Cl with other halides, and the axial methyl group with an acetyl group. This has resulted in a series of Fe(III) TBP complexes modelled in their IS and high-spin (HS) states. Lighter ligands -N and -F stabilize the complex in the HS state, while the magnetically anisotropic IS state is stabilized by -P and -As at the axial site, and -Cl, -Br, and -I at the equatorial site. Larger magnetic anisotropies appear for complexes with nearly degenerate ground electronic states that are well separated from the higher excited states. This requirement, largely controlled by the d-orbital splitting pattern due to the changing ligand field, is achieved with a certain combination of axial and equatorial ligands, such as -P and -Br, -As and -Br, and -As and -I. In most cases, the acetyl group at the axial site enhances the magnetic anisotropy compared to its methyl counterpart. In contrast, the presence of -I at the equatorial site compromises the uniaxial type of anisotropy of the Fe(III) complex leading to an enhanced rate of quantum tunneling of magnetization.

Importance of Dispersion in the Molecular Geometries of Mn(III) Spin-Crossover Complexes.

The computational investigation of the molecular geometries of a pair of manganese(III) spin-crossover complexes is reported. For the geometry of the quintet high-spin state, density functionals significantly overestimate Mn-Namine bond distances, although the geometry for the triplet intermediate-spin state is well described. Comparisons with several wave function-based methods demonstrate that this error is due to the limited ability of commonly used density functionals to recover dispersion beyond a certain extent. Among the methods employed for geometry optimization, restricted open-shell Møller-Plesset perturbation theory (MP2) appropriately describes the high-spin geometry but results in a slightly shorter Mn-O distance in both spin states. On the other hand, extended multistate complete active space second-order perturbation theory (XMS-CASPT2) provides a good description of the geometry for the intermediate-spin state but also sufficiently recovers dispersion, performing well for the high-spin state. Despite the fact that the electronic structure of both spin states is dominated by one-electron configuration, XMS-CASPT2 offers a balanced approach, leading to molecular geometries with much better agreement with experiment than MP2 and DFT. A scan along the Mn-Namine bond demonstrates that for these complexes coupled cluster methods (i.e., DLPNO-CCSD(T)) also yield bond distances in agreement with experiment while multiconfiguration pair density functional theory (MC-PDFT) is unable to recover dispersion well enough, analogous to single-reference DFT.

CASPT2 molecular geometries of Fe(II) spin-crossover complexes.

Using fully internally contracted (FIC)-CASPT2 analytical gradients, geometry optimizations of spin-crossover complexes are reported. This approach is tested on a series of Fe(II) complexes with different sizes, ranging from 13 to 61 atoms. A combination of active space and basis set choices are employed to investigate their role in determining reliable molecular geometries. The reported strategy demonstrates that a wave function-based level of theory can be used to optimize the geometries of metal complexes in reasonable times and enables one to treat the molecular geometry and electronic structure of the complexes using the same level of theory. For a series of smaller Fe(II) SCO complexes, strong field ligands in the LS state result in geometries with the largest differences between DFT and CASPT2; however, good agreement overall is observed between DFT and CASPT2. For the larger complexes, moderate sized basis sets yield geometries that compare well with DFT and available experimental data. We recommend using the (10e,12o) active space since convergence to a minimum structure was more efficient than with truncated active spaces despite having similar Fe-ligand bond distances.

A single-centre observational cohort study to evaluate volume and severity of emergency general surgery admissions during the COVID-19 pandemic: Is there a "lockdown" effect?

INTRODUCTION: The COVID-19 pandemic has led to changes in NHS surgical service provision, including reduced elective surgical and endoscopic activity, with only essential emergency surgery being undertaken. This, combined with the government-imposed lockdown, may have impacted on patient attendance, severity of surgical disease, and outcomes. The aim of this study was to investigate a possible 'lockdown' effect on the volume and severity of surgical admissions and their outcomes. METHODS: Two separate cohorts of adult emergency general surgery inpatient admissions 30 days immediately before (February 16, 2020 to March 15, 2020), and after UK government advice (March 16, 2020 to April 15, 2020). Data were collected relating to patient characteristics, severity of disease, clinical outcomes, and compared between these groups. RESULTS: Following lockdown, a significant reduction in median daily admissions from 7 to 3 per day (p < 0.001) was observed. Post-lockdown patients were significantly older, frailer with higher inflammatory indices and rates of acute kidney injury, and also were significantly more likely to present with gastrointestinal cancer, obstruction, and perforation. Patients had significantly higher rates of Clavien-Dindo Grade ≥3 complications (p = 0.001), all cause 30-day mortality (8.5% vs. 2.9%, p = 0.028), but no significant difference was observed in operative 30-day mortality. CONCLUSION: There appears to be a "lockdown" effect on general surgical admissions with a profound impact; fewer surgical admissions, more acutely unwell surgical patients, and an increase in all cause 30-day mortality. Patients should be advised to present promptly with gastrointestinal symptoms, and this should be reinforced for future lockdowns during the pandemic.

Role of Substituents at 3-position of Thienylethynyl Spacer on Electronic Properties in Diruthenium(II) Organometallic Wire-like Complexes.

A series of organometallic complexes [Cl(dppe)2 Ru-C≡C-(3-R-C4 H2 S)-C≡C-Ru(dppe)2 Cl] (3-R-C4 H2 S=3-substituted thienyl moiety; R=-H, -C2 H5 , -C3 H7 , -C4 H9 , -C6 H13 , -OMe, -CN in 5 a-5 g respectively) have been synthesized by systematic variation of 3-substituents at the thienylethynyl bridging unit. The diruthenum(II) wire-like complexes (5 a-5 g) have been achieved by the reaction of thienylethynyl bridging units, HC≡C-(3-R-C4 H2 S)-C≡CH (4 a-4 g) with cis-[Ru(dppe)2 Cl2 ]. The wire-like diruthenium(II) complexes undergo two consecutive electrochemical oxidation processes in the potential range of 0.0 - 0.8 V. Interestingly, the wave separation between the two redox waves is greatly influenced by the substituents at the 3-position of the thienylethynyl. Thus, the substitution on 3-position of the thienylethynyl bridging unit plays a pivotal role for tuning the electronic properties. To understand the electronic behavior, density functional theory (DFT) calculations of the selected diruthenium wire-like complexes (5 a-5 e) with different alkyl appendages are performed. The theoretical data demonstrate that incorporation of alkyl groups to the thienylethynyl entity leaves unsymmetrical spin densities, thus affecting the electronic properties. The voltammetric features of the other two Ru(II) alkynyl complexes 5 f and 5 g (with -OMe and -CN group respectively) show an apparent dependence on the electronic properties. The electronic properties in the redox conjugate, (5 a+ ) with Kc of 3.9×106 are further examined by UV-Vis-NIR and FTIR studies, showing optical responses in NIR region along with changes in "-Ru-C≡C-" vibrational stretching frequency. The origin of the observed electronic transition has been assigned based on time-dependent DFT (TDDFT) calculations.

Light-Induced Spin Crossover in an Intermediate-Spin Penta-Coordinated Iron(III) Complex.

(PMe3)2FeCl3 is an Fe(III) complex that exists in the intermediate-spin ground state in a distorted trigonal bipyramidal geometry. An electronic state with high-spin configuration lies in close vicinity to the ground state, making it a potential spin crossover candidate. A mechanistic account of the spin crossover from the lowest quartet state (Q0) to the lowest sextet state (S1) of this complex is provided by exploring both thermal and light-induced pathways. The presence of a large barrier between the two spin states suggests a possible thermal spin crossover at a rather high temperature. The light-induced spin crossover is investigated by employing complete active space self-consistent field calculations together with dynamic correlation and spin-orbit coupling for the lowest seven quartet and lowest five sextet states. The system in the Q0 state upon light absorption is excited to the optically bright Q4 LMCT state. By following minimum energy pathways along the electronic states, two light-induced pathways for spin crossover are identified. From the Q4 state, the system can photo-regenerate the ground intermediate-spin state (Q0) through an internal conversion of Q4/Q3 followed by Q3/S1 and S1/Q0 intersystem crossings. In an alternate route, through Q4/S2 intersystem crossing followed by S2/S1 internal conversion, the system can complete the spin crossover from the Q0 to S1 state.

Visible-Light-Activated Divergent Reactivity of Dienones: Dimerization in Neat Conditions and Regioselective E to Z Isomerization in the Solvent.

2,4-Dienones undergo visible-light-promoted, photocatalyst-free dimerization in neat conditions to provide cyclohexene derivatives stereoselectively through cascade rearrangement pathways, whereas regioselective E → Z isomerization of the more dienophilic double bond takes place exclusively in nitromethane. On the basis of intermediate isolation and computational DFT studies, the dimerization reaction is proposed to proceed via s-trans to s-cis isomerization/regioselective E → Z isomerization/Diels-Alder cycloaddition.

Ab initio investigation of magnetic anisotropy in intermediate spin iron(iii) complexes.

Mononuclear Fe(iii) complexes commonly exist in high-spin or low-spin states, whereas their occurrence in the intermediate-spin state (S = 3/2) is scarce. The magnetic anisotropy in two trigonal-bipyramidal mononuclear Fe(iii) complexes, ( P M e 3 ) 2 F e C l 3 (1) and ( P M e 2 P h ) 2 F e C l 3 (2), in their intermediate-spin ground state has been examined by ab initio electronic structure calculations. The calculations successfully reproduce the experimental magnetic anisotropic barrier, U eff in 1 (81 cm-1) and 2 (42 cm-1), which is shown to arise due to thermally assisted quantum tunneling of magnetization from the second Kramer's doublets. The magnetic anisotropy in both the complexes is found to be significantly influenced by the axial ligands, while the equatorial ligands have negligible contribution. The large reduction in U eff of 2 has been shown to arise due to the phenyl groups, which results in the lifting of orbital degeneracy of e″ and e' frontier orbitals and leads to a net quenching of the orbital angular momentum of the metal center causing a diminished spin-orbit splitting in 2. While the crystal structure of 2 shows two phenyl rings out of plane to each other, the present study discovered another stable conformation of 2, where the two phenyl rings are in the same plane (2a). Unlike 2, the planarity of the two phenyl rings in 2a restores the degeneracy of the frontier orbitals, thereby increasing the spin-orbit splitting and a consequent rise in U eff from 42 to 80 cm-1 in 2a.

Synthesis, structure, and photophysical and electrochemical properties of Ru(ii) complexes of arylene-vinylene terpyridyl conjugates.

A series of arylene-vinylene π-conjugated terpyridyl ruthenium(ii) complexes, [Ru(PPh3)2Cl(tpy-C6H4-CH[double bond, length as m-dash]CH-Ar)][PF6] (1-4; tpy = 2,2':6',2''-terpyridyl, where Ar = phenyl, tolyl, 1-naphthyl and 9-anthracenyl as substituents at the 4' position of tpy), have been synthesized and characterized by multinuclear NMR, IR, HRMS and single crystal X-ray crystallography. The influence of the electronic nature of arylene groups on their photophysical and electrochemical properties has been investigated to understand the electronic interaction between the metal-organic redox centers. Furthermore, a σ-donor phenylacetylide group has been incorporated to accomplish [Ph-C[triple bond, length as m-dash]C-Ru(PPh3)2(tpy-C6H4-CH[double bond, length as m-dash]CH-Ar)][PF6] (5-8) complexes by the substitution of a coordinated chloride ligand and to investigate the change in their redox and photophysical properties. DFT studies have been performed to gain an insight into their electronic properties by determining the HOMO-LUMO energy levels and frontier molecular orbitals of all the synthesized Ru(ii) complexes.

Diruthenium(ii)-capped oligothienylethynyl bridged highly soluble organometallic wires exhibiting long-range electronic coupling.

Organometallic molecular wires with π-conjugation along their molecular backbones are of considerable interest for application in molecular-scale electronics. In this regard, thienylethynyl-based π-conjugated oligomers of three, five and seven thienylethynyl units with -C[triple bond, length as m-dash]C-H termini have been successfully synthesized through stepwise Pd(0)/Cu(i)-catalyzed Sonogashira coupling. The corresponding highly soluble diruthenium(ii) diacetylide complexes (O1-Ru2, O3-Ru2, O5-Ru2 and O7-Ru2, respectively) have been prepared by the reaction of cis-Ru(dppe)2Cl2 and NaPF6 in DCM with the corresponding rigid rod-like thienylethynyl oligomers with one, three, five and seven thienylethynyl π-conjugated segments containing alkynyl termini (O1, O3, O5 and O7). These Ru(ii)-Cl capped diacetylide complexes have been further functionalized by incorporating a phenylacetynyl moiety to afford [Ru(ii)-C[triple bond, length as m-dash]C-Ph]-capped diacetylide organometallic wires (O1-Ru2-Ph, O3-Ru2-Ph, O5-Ru2-Ph and O7-Ru2-Ph). The photophysical properties of the highly soluble thienylethynyl-based oligomers and Ru(ii)-organometallic wires have been explored to understand their electronic properties. Electrochemical studies of the binuclear ruthenium(ii)-alkynyl complexes showed highly interesting results, revealing long-range electrochemical communication between the two remote Ru(ii) termini connected even with five and seven thienylethynyl units. DFT computational studies further support the long range electrochemical communication between the redox active metal termini through heavy participation of the thienylethynyl bridge in the corresponding mono-oxidized mixed valence species of the organometallic wire-like complexes.

Heavy ligand atom induced large magnetic anisotropy in Mn(ii) complexes.

In the search for single molecule magnets, metal ions are considered pivotal towards achieving large magnetic anisotropy barriers. In this context, the influence of ligands with heavy elements, showing large spin-orbit coupling, on magnetic anisotropy barriers was investigated using a series of Mn(ii)-based complexes, in which the metal ion did not have any orbital contribution. The mixing of metal and ligand orbitals was achieved by explicitly correlating the metal and ligand valence electrons with CASSCF calculations. The CASSCF wave functions were further used for evaluating spin-orbit coupling and zero-field splitting parameters for these complexes. For Mn(ii) complexes with heavy ligand atoms, such as Br and I, several interesting inter-state mixings occur via the spin-orbit operator, which results in large magnetic anisotropy in these Mn(ii) complexes.