Mechanistic insights into radical formation and functionalization in copper/N-fluorobenzenesulfonimide radical-relay reactions.

Copper-catalysed radical-relay reactions that employ N-fluorobenzenesulfonimide (NFSI) as the oxidant have emerged as highly effective methods for C(sp3)-H functionalization. Herein, computational studies are paired with experimental data to investigate a series of key mechanistic features of these reactions, with a focus on issues related to site-selectivity, enantioselectivity, and C-H substrate scope. (1) The full reaction energetics of enantioselective benzylic C-H cyanation are probed, and an adduct between Cu and the N-sulfonimidyl radical (˙NSI) is implicated as the species that promotes hydrogen-atom transfer (HAT) from the C-H substrate. (2) Benzylic versus 3° C-H site-selectivity is compared with different HAT reagents: Cu/˙NSI, ˙OtBu, and Cl˙, and the data provide insights into the high selectivity for benzylic C-H bonds in Cu/NFSI-catalyzed C-H functionalization reactions. (3) The energetics of three radical functionalization pathways are compared, including radical-polar crossover (RPC) to generate a carbocation intermediate, reductive elimination from a formal CuIII organometallic complex, and radical addition to a Cu-bound ligand. The preferred mechanism is shown to depend on the ligands bound to copper. (4) Finally, the energetics of three different pathways that convert benzylic C-H bonds into benzylic cations are compared, including HAT/ET (ET = electron transfer), relevant to the RPC mechanism with Cu/NFSI; hydride transfer, involved in reactions with high-potential quinones; and sequential ET/PT/ET (PT = proton transfer), involved in catalytic photoredox reactions. Collectively, the results provide mechanistic insights that establish a foundation for further advances in radical-relay C-H functionalization reactions.

Understanding Antiferromagnetic and Ligand Field Effects on Spin Crossover in a Triple-Decker Dimeric Cr(II) Complex.

Two possible explanations for the temperature dependence of spin-crossover (SCO) behavior in the dimeric triple-decker Cr(II) complex ([(η5-C5Me5)Cr(µ2:η5-P5)Cr(η5-C5Me5)]+) have been offered. One invokes variations in antiferromagnetic interactions between the two Cr(II) ions, whereas the other posits the development of a strong ligand-field effect favoring the low-spin ground state. We perform multireference electronic structure calculations based on the multiconfiguration pair-density functional theory to resolve these effects. We find quintet, triplet, and singlet electronic ground states, respectively, for the experimental geometries at high, intermediate, and low temperatures. The ground-state transition from quintet to triplet at an intermediate temperature derives from increased antiferromagnetic interactions between the two Cr(II) ions. By contrast, the ground-state transition from triplet to singlet at low temperature can be attributed to increased ligand-field effects, which dominate with continued variations in antiferromagnetic coupling. This study provides quantitative detail for the degree to which these two effects can act in concert for the observed SCO behavior in this complex and others subject to temperature-dependent variations in geometry.

Radical ring-opening polymerization of sustainably-derived thionoisochromanone.

We present the synthesis, characterization and radical ring-opening polymerization (rROP) capabilities of thionoisochromanone (TIC), a fungi-derivable thionolactone. TIC is the first reported six-membered thionolactone to readily homopolymerize under free radical conditions without the presence of a dormant comonomer or repeated initiation. Even more, the resulting polymer is fully degradable under mild, basic conditions. Computations providing molecular-level insights into the mechanistic and energetic details of polymerization identified a unique S,S,O-orthoester intermediate that leads to a sustained chain-end. This sustained chain-end allowed for the synthesis of a block copolymer of TIC and styrene under entirely free radical conditions without explicit radical control methods such as reversible addition-fragmentation chain transfer polymerization (RAFT). We also report the statistical copolymerization of ring-retained TIC and styrene, confirmed by elemental analysis and energy-dispersive X-ray spectroscopy (EDX). Computations into the energetic details of copolymerization indicate kinetic drivers for ring-retaining behavior. This work provides the first example of a sustainable feedstock for rROP and provides the field with the first six-membered monomer susceptible to rROP, expanding the monomer scope to aid our fundamental understanding of thionolactone rROP behavior.

Correction: Radical ring-opening polymerization of sustainably-derived thionoisochromanone.

[This corrects the article DOI: 10.1039/D2SC06040J.].

Metal-Carbodithioate-Based 3D Semiconducting Metal-Organic Framework: Porous Optoelectronic Material for Energy Conversion.

Solar energy conversion requires the working compositions to generate photoinduced charges with high potential and the ability to deliver charges to the catalytic sites and/or external electrode. These two properties are typically at odds with each other and call for new molecular materials with sufficient conjugation to improve charge conductivity but not as much conjugation as to overly compromise the optical band gap. In this work, we developed a semiconducting metal-organic framework (MOF) prepared explicitly through metal-carbodithioate "(-CS2)nM" linkage chemistry, entailing augmented metal-linker electronic communication. The stronger ligand field and higher covalent character of metal-carbodithioate linkages─when combined with spirofluorene-derived organic struts and nickel(II) ion-based nodes─provided a stable, semiconducting 3D-porous MOF, Spiro-CS2Ni. This MOF lacks long-range ordering and is defined by a flexible structure with non-aggregated building units, as suggested by reverse Monte Carlo simulations of the pair distribution function obtained from total scattering experiments. The solvent-removed "closed pore" material recorded a Brunauer-Emmett-Teller area of ∼400 m2/g, where the "open pore" form possesses 90 wt % solvent-accessible porosity. Electrochemical measurements suggest that Spiro-CS2Ni possesses a band gap of 1.57 eV (σ = 10-7 S/cm at -1.3 V bias potential), which can be further improved by manipulating the d-electron configuration through an axial coordination (ligand/substrate), the latter of which indicates usefulness as an electrocatalyst and/or a photoelectrocatalyst (upon substrate binding). Transient-absorption spectroscopy reveals a long-lived photo-generated charge-transfer state (τCR = 6.5 µs) capable of chemical transformation under a biased voltage. Spiro-CS2Ni can endure a compelling range of pH (1-12 for weeks) and hours of electrochemical and photoelectrochemical conditions in the presence of water and organic acids. We believe this work provides crucial design principles for low-density, porous, light-energy-conversion materials.

Localized Active Space-State Interaction: a Multireference Method for Chemical Insight.

Multireference electronic structure methods, like the complete active space (CAS) self-consistent field model, have long been used to characterize chemically interesting processes. Important work has been done in recent years to develop modifications having a lower computational cost than CAS, but typically these methods offer no more chemical insight than that from the CAS solution being approximated. In this paper, we present the localized active space-state interaction (LASSI) method that can be used not only to lower the intrinsic cost of the multireference calculation but also to improve interpretability. The localized active space (LAS) approach utilizes the local nature of the electron-electron correlation to express a composite wave function as an antisymmetrized product of unentangled wave functions in local active subspaces. LASSI then uses these LAS states as a basis from which to express complete molecular wave functions. This not only makes the molecular wave function more compact but also permits flexibility in choosing those states to be included in the basis. Such selective inclusion of states translates to the selective inclusion of specific types of interactions, thereby allowing a quantitative analysis of these interactions. We demonstrate the use of LASSI to study charge migration and spin-flip excitations in multireference organic molecules. We also compute the J coupling parameter for a bimetallic compound using various LAS bases to construct the Hamiltonian to provide insights into the coupling mechanism.

Stereoregular functionalized polysaccharides via cationic ring-opening polymerization of biomass-derived levoglucosan.

We report the facile synthesis and characterization of 1,6-α linked functional stereoregular polysaccharides from biomass-derived levoglucosan via cationic ring-opening polymerization (cROP). Levoglucosan is a bicyclic acetal with rich hydroxyl functionality, which can be synthetically modified to install a variety of pendant groups for tailored properties. We have employed biocompatible and recyclable metal triflate catalysts - scandium and bismuth triflate - for green cROP of levoglucosan derivatives, even at very low catalyst loadings of 0.5 mol%. Combined experimental and computational studies provided key kinetic, thermodynamic, and mechanistic insights into the cROP of these derivatives with metal triflates. Computational studies reveal that ring-opening of levoglucosan derivatives is preferred at the 1,6 anhydro linkage and cROP proceeds in a regio- and stereo-specific manner to form 1,6-α glycosidic linkages. DFT calculations also show that biocompatible metal triflates efficiently coordinate with levoglucosan derivatives as compared to the highly toxic PF5 used previously. Post-polymerization modification of levoglucosan-based polysaccharides is readily performed via UV-initiated thiol-ene click reactions. The reported levoglucosan based polymers exhibit good thermal stability (T d > 250 °C) and a wide glass transition temperature (T g) window (<-150 °C to 32 °C) that is accessible with thioglycerol and lauryl mercaptan pendant groups. This work demonstrates the utility of levoglucosan as a renewably-derived scaffold, enabling facile access to tailored polysaccharides that could be important in many applications ranging from sustainable materials to biologically active polymers.

Development of a Highly Responsive Organofluorine Temperature Sensor for 19F Magnetic Resonance Applications.

Temperature can affect many biological and chemical processes within a body. During in vivo measurements, varied temperature can impact the accurate quantification of additional abiotic factors such as oxygen. During magnetic resonance imaging (MRI) measurements, the temperature of the sample can increase with the absorption of radiofrequency energy, which needs to be well-regulated for thermal therapies and long exposure. To address this potentially confounding effect, temperature can be probed intentionally using reporter molecules to determine the temperature in vivo. This work describes a combined experimental and computational approach for the design of fluorinated molecular temperature sensors with the potential to improve the accuracy and sensitivity of 19F MRI-based temperature monitoring. These fluorinated sensors are being developed to overcome the temperature sensitivity and tissue limitations of the proton resonance frequency (10 × 10-3 ppm °C-1), a standard parameter used for temperature mapping in MRI. Here, we develop (perfluoro-[1,1'-biphenyl]-4,4'-diyl)bis((heptadecafluorodecyl)sulfane), which has a nearly 2-fold increase in temperature responsiveness, compared to the proton resonance frequency and the 19F MRI temperature sensor perfluorotributylamine, when tested under identical NMR conditions. While 19F MRI is in the early stages of translation into clinical practice, development of alternative sensors with improved diagnostic abilities will help advance the development and incorporation of fluorine magnetic resonance techniques for clinical use.

Defining the Macromolecules of Tomorrow through Synergistic Sustainable Polymer Research.

Transforming how plastics are made, unmade, and remade through innovative research and diverse partnerships that together foster environmental stewardship is critically important to a sustainable future. Designing, preparing, and implementing polymers derived from renewable resources for a wide range of advanced applications that promote future economic development, energy efficiency, and environmental sustainability are all central to these efforts. In this Chemical Reviews contribution, we take a comprehensive, integrated approach to summarize important and impactful contributions to this broad research arena. The Review highlights signature accomplishments across a broad research portfolio and is organized into four wide-ranging research themes that address the topic in a comprehensive manner: Feedstocks, Polymerization Processes and Techniques, Intended Use, and End of Use. We emphasize those successes that benefitted from collaborative engagements across disciplinary lines.

Superradiance and Directional Exciton Migration in Metal-Organic Frameworks.

Crystalline metal-organic frameworks (MOFs) are promising synthetic analogues of photosynthetic light-harvesting complexes (LHCs). The precise assembly of linkers (organic chromophores) around the topology-defined pores offers the evolution of unique photophysical behaviors that are reminiscence of LHCs. These include MOF excited states with photoabsorbed energy that is spatially dispersed over multiple linkers defining the molecular excitons. The multilinker molecular excitons display superradiance─a hallmark of coupled oscillators seen in LHCs─with radiative rate constant (krad) exceeding that of a single linker. Our theoretical model and experimental results on three zirconium MOFs, namely, PCN-222(Zn), NU-1000, and SIU-100, with similar topology but varying linkers suggest that the size of such molecular excitons depends on the electronic symmetry of the linker. This multilinker exciton model effectively predicts the energy transfer rate constant; corresponding single-step exciton hopping time, ranging from a few picoseconds in SIU-100 and NU-1000 to a few hundreds of picoseconds in PCN-222(Zn), matches well with the experimental data. The model also predicts the anisotropy of exciton displacement with preferential migration along the crystallographic c-axis. Overall, these findings establish various missing links defining the exciton size and dynamics in MOF-assembled linkers. The understandings will provide design principles, especially, positioning the catalysts or electrode relative to the linker orientation for low-density solar energy conversion systems.

The Molecular Path Approaching the Active Site in Catalytic Metal-Organic Frameworks.

How molecules approach, bind at, and release from catalytic sites is key to heterogeneous catalysis, including for emerging metal-organic framework (MOF)-based catalysts. We use in situ synchrotron X-ray scattering analysis to evaluate the dominant binding sites for reagent and product molecules in the vicinity of catalytic Ni-oxo clusters in NU-1000 with different surface functionalization under conditions approaching those used in catalysis. The locations of the reagent and product molecules within the pores can be linked to the activity for ethylene hydrogenation. For the most active catalyst, ethylene reagent molecules bind close to the catalytic clusters, but only at temperatures approaching experimentally observed onset of catalysis. The ethane product molecules favor a different binding location suggesting that the product is readily released from the active site. An unusual guest-dependence of the framework negative thermal expansion is documented. We hypothesize that reagent and product binding sites reflect the pathway through the MOF to the active site and can be used to identify key factors that impact the catalytic activity.

Localized Active Space Pair-Density Functional Theory.

Accurate quantum chemical methods for the prediction of spin-state energy gaps for strongly correlated systems are computationally expensive and scale poorly with the size of the system. This makes calculations for many experimentally interesting molecules impractical even with abundant computational resources. Previous work has shown that the localized active space (LAS) self-consistent field (SCF) method can be an efficient way to obtain multiconfiguration SCF wave functions of comparable quality to the corresponding complete active space (CAS) ones. To obtain quantitative results, a post-SCF method is needed to estimate the complete correlation energy. One such method is multiconfiguration pair-density functional theory (PDFT), which calculates the energy based on the density and on-top pair density obtained from a multiconfiguration wave function. In this work, we introduce localized-active-space PDFT, which uses a LAS wave function for subsequent PDFT calculations. The method is tested by computing spin-state energies and gaps in conjugated organic molecules and a bimetallic compound and comparing to the corresponding CAS-PDFT values.

Copper-zirconia interfaces in UiO-66 enable selective catalytic hydrogenation of CO2 to methanol.

Molecular interactions with both oxides and metals are essential for heterogenous catalysis, leading to remarkable synergistic impacts on activity and selectivity. Here, we show that the direct link between the two phases (and not merely being together) is required to selectively hydrogenate CO2 to methanol on catalysts containing Cu and ZrO2. Materials consisting of isolated Cu particles or atomically dispersed Cu-O-Zr sites only catalyze the reverse water-gas shift reaction. In contrast, a metal organic framework structure (UiO-66) with Cu nanoparticles occupying missing-linker defects maximizes the fraction of metallic Cu interfaced to ZrO2 nodes leading to a material with high adsorption capacity for CO2 and high activity and selectivity for low-temperature methanol synthesis.

Isomerization and Selective Hydrogenation of Propyne: Screening of Metal-Organic Frameworks Modified by Atomic Layer Deposition.

Various metal oxide clusters upward of 8 atoms (Cu, Cd, Co, Fe, Ga, Mn, Mo, Ni, Sn, W, Zn, In, and Al) were incorporated into the pores of the metal-organic framework (MOF) NU-1000 via atomic layer deposition (ALD) and tested via high-throughput screening for catalytic isomerization and selective hydrogenation of propyne. Cu and Co were found to be the most active for propyne hydrogenation to propylene, and synergistic bimetallic combinations of Co and Zn, along with standalone Zn and Cd, were established as the most active for conversion to the isomerized product, propadiene. The combination of Co and Zn in NU-1000 diminished the propensity for full hydrogenation to propane as well as coking compared to its individual components. This study highlights the potential for high-throughput screening to survey monometallic and bimetallic cluster combinations that best affect the efficient transformation of small molecules, while discerning mechanistic differences in isomerization and hydrogenation by different metals.

Mechanistic Insight into the Stereoselective Cationic Polymerization of Vinyl Ethers.

The control of the tacticity of synthetic polymers enables the realization of emergent physical properties from readily available starting materials. While stereodefined polymers derived from nonpolar vinyl monomers can be efficiently prepared using early transition metal catalysts, general methods for the stereoselective polymerization of polar vinyl monomers remain underdeveloped. We recently demonstrated asymmetric ion pairing catalysis as an effective approach to achieve stereoselective cationic polymerization of vinyl ethers. Herein, we provide a deeper understanding of stereoselective ion-pairing polymerization through comprehensive experimental and computational studies. These findings demonstrate the importance of ligand deceleration effects for the identification of reaction conditions that enhance stereoselectivity, which was supported by computational studies that identified the solution-state catalyst structure. An evaluation of monomer substrates with systematic variations in steric parameters and functional group identities established key structure-reactivity relationships for stereoselective homo- and copolymerization. Expansion of the monomer scope to include enantioenriched vinyl ethers enabled the preparation of an isotactic poly(vinyl ether) with the highest stereoselectivity (95.1% ± 0.1 meso diads) reported to date, which occurred when monomer and catalyst stereochemistry were fully matched under a triple diastereocontrol model. The more complete understanding of stereoselective cationic polymerization reported herein offers a foundation for the design of improved catalytic systems and for the translation of isotactic poly(vinyl ether)s to applied areas.

First Principles Nonadiabatic Excited-State Molecular Dynamics in NWChem.

Computational simulation of nonadiabatic molecular dynamics is an indispensable tool for understanding complex photoinduced processes such as internal conversion, energy transfer, charge separation, and spatial localization of excitons, to name a few. We report an implementation of the fewest-switches surface-hopping algorithm in the NWChem computational chemistry program. The surface-hopping method is combined with linear-response time-dependent density functional theory calculations of adiabatic excited-state potential energy surfaces. To treat quantum transitions between arbitrary electronic Born-Oppenheimer states, we have implemented both numerical and analytical differentiation schemes for derivative nonadiabatic couplings. A numerical approach for the time-derivative nonadiabatic couplings together with an analytical method for calculating nonadiabatic coupling vectors is an efficient combination for surface-hopping approaches. Additionally, electronic decoherence schemes and a state reassigned unavoided crossings algorithm are implemented to improve the accuracy of the simulated dynamics and to handle trivial unavoided crossings. We apply our code to study the ultrafast decay of photoexcited benzene, including a detailed analysis of the potential energy surface, population decay timescales, and vibrational coordinates coupled to the excitation dynamics. We also study the photoinduced dynamics in trans-distyrylbenzene. This study provides a baseline for future implementations of higher-level frameworks for simulating nonadiabatic molecular dynamics in NWChem.

Exploring the Effects of Node Topology, Connectivity, and Metal Identity on the Binding of Nerve Agents and Their Hydrolysis Products in Metal-Organic Frameworks.

Recent studies have shown that metal-organic frameworks (MOFs) built from hexanuclear M(IV) oxide cluster nodes are effective catalysts for nerve agent hydrolysis, where the properties of the active sites on the nodes can strongly influence the reaction energetics. The connectivity and metal identity of these M6 nodes can be easily tuned, offering extensive opportunities for computational screening to predict promising new materials. Thus, we used density functional theory (DFT) to examine the effects of node topology, connectivity, and metal identity on the binding energies of multiple nerve agents and their corresponding hydrolysis products. By computing an optimization metric based on the relative binding strengths of key hydrolysis reaction species (water, agent, and bidentate-bound products), we predicted optimal M6 nodes for hydrolyzing specific nerve agent and simulant molecules, where our results are in qualitative agreement with observed experimental trends. This analysis highlighted the notion that no single metal or node topology is optimal for all possible organophosphates, suggesting that MOFs should be selected based on the agent of interest. Using the large amount of data generated from our DFT calculations, we then derived quantitative structure-activity relationship (QSAR) models to help explain the complex trends observed in the binding energies. Through linear regression, we identified the most important descriptors for describing the binding of nerve agents and their hydrolysis products to M6 nodes. These results suggested that both molecular and node properties, including both structural and chemical features, collectively contribute to the binding energetics. By performing a thorough statistical analysis, we showed that our QSAR models are capable of making quantitatively accurate binding energy predictions for nerve agents and their hydrolysis products in a wide variety of M(IV)-MOFs. The insights gained herein can be used to guide future experiments for the synthesis of MOFs with enhanced catalytic activity for organophosphate hydrolysis.

Site-Selective Copper-Catalyzed Azidation of Benzylic C-H Bonds.

Site selectivity represents a key challenge for non-directed C-H functionalization, even when the C-H bond is intrinsically reactive. Here, we report a copper-catalyzed method for benzylic C-H azidation of diverse molecules. Experimental and density functional theory studies suggest the benzyl radical reacts with a CuII-azide species via a radical-polar crossover pathway. Comparison of this method with other C-H azidation methods highlights its unique site selectivity, and conversions of the benzyl azide products into amine, triazole, tetrazole, and pyrrole functional groups highlight the broad utility of this method for target molecule synthesis and medicinal chemistry.

Copper-catalysed benzylic C-H coupling with alcohols via radical relay enabled by redox buffering.

Cross-coupling reactions enable rapid, convergent synthesis of diverse molecules and provide the foundation for modern chemical synthesis. The most widely used methods employ sp2-hybridized coupling partners, such as aryl halides or related pre-functionalized substrates. Here, we demonstrate copper-catalysed oxidative cross coupling of benzylic C-H bonds with alcohols to afford benzyl ethers, enabled by a redox-buffering strategy that maintains the activity of the copper catalyst throughout the reaction. The reactions employ the C-H substrate as the limiting reagent and exhibit broad scope with respect to both coupling partners. This approach to direct site-selective functionalization of C(sp3)-H bonds provides the basis for efficient three-dimensional diversification of organic molecules and should find widespread utility in organic synthesis, particularly for medicinal chemistry applications.

Correlating Electronic Structure and Magnetic Anisotropy in Actinide Complexes [An(COT)2], AnIII/IV = U, Np, and Pu.

The electronic structures and magnetic anisotropies for compounds [An(COT)2] (An = UIII/UIV, NpIII/NpIV and PuIII/PuIV, COT = cyclooctatetraene) are characterized using scalar relativistic density functional theory calculations and second-order perturbation theory based on a complete active space self-consistent field reference including spin-orbit coupling. The degree of participation of 5f orbitals in actinide-ligand bonding and the associated metal-ligand covalency is found to trend as U > Np ≥ Pu for both the tetra-positive and tripositive An complexes. A spin-Hamiltonian analysis indicates only weak single-molecule magnet (SMM) characteristics for [U(COT)2]- and [Np(COT)2] complexes and no significant SMM behavior for the other complexes. The weak SMM behavior in [U(COT)2]- and [Np(COT)2] is attributed to a subtle interplay between local symmetry and ligand-field splitting. Such a result suggests that magnetic anisotropy in 5f3 ions can be modulated in general by electrostatic ligand field design. In particular, σ-donor ligands oriented 180 degrees relative to one another will have a maximal influence on the 5f-orbital ligand field splitting, while π donors like cyclopentadiene and COT generate ligand field influences that have more acute angles associated with corresponding atoms on the individual ligands. These observations rationalize the differences in SMM characteristics for [U(BcMe)3] (BcMe- = dihydrobis(methylimidazolyl)borate) and [U(BpMe)3] (BpMe- = dihydrobis(methylpyrazolyl)borate) and indicate strategies to design new actinide-based SMMs with high magnetic relaxation barriers.