Coordination of copper within a crystalline carbon nitride and its catalytic reduction of CO2.

Inherently disordered structures of carbon nitrides have hindered an atomic level tunability and understanding of their catalytic reactivity. Starting from a crystalline carbon nitride, poly(triazine imide) or PTI/LiCl, the coordination of copper cations to its intralayer N-triazine groups was investigated using molten salt reactions. The reaction of PTI/LiCl within CuCl or eutectic KCl/CuCl2 molten salt mixtures at 280 to 450 °C could be used to yield three partially disordered and ordered structures, wherein the Cu cations are found to coordinate within the intralayer cavities. Local structural differences and the copper content, i.e., whether full or partial occupancy of the intralayer cavity occurs, were found to be dependent on the reaction temperature and Cu-containing salt. Crystallites of Cu-coordinated PTI were also found to electrophoretically deposit from aqueous particle suspensions onto either graphite or FTO electrodes. As a result, electrocatalytic current densities for the reduction of CO2 and H2O reached as high as ∼10 to 50 mA cm-2, and remained stable for >2 days. Selectivity for the reduction of CO2 to CO vs. H2 increases for thinner crystals as well as for when two Cu cations coordinate within the intralayer cavities of PTI. Mechanistic calculations have also revealed the electrocatalytic activity for CO2 reduction requires a smaller thermodynamic driving force with two neighboring Cu atoms per cavity as compared to a single Cu atom. These results thus establish a useful synthetic pathway to metal-coordination in a crystalline carbon nitride and show great potential for mediating stable CO2 reduction at sizable current densities.

Electronic Structure and Photophysics of Low Spin d5 Metallocenes.

The electronic structure and photophysics of two low spin metallocenes, decamethylmanganocene (MnCp*2) and decamethylrhenocene (ReCp*2), were investigated to probe their promise as photoredox reagents. Computational studies support the assignment of 2E2 ground state configurations and low energy ligand-to-metal charge transfer transitions for both complexes. Weak emission is observed at room temperature for ReCp*2 with τ = 1.8 ns in pentane, whereas MnCp*2 is not emissive. Calculation of the excited state reduction potentials for both metallocenes reveal their potential potency as excited state reductants (E°'([MnCp*2]+/0*) = -3.38 V and E°'([ReCp*2]+/0*) = -2.61 V vs Fc+/0). Comparatively, both complexes exhibit mild potentials for photo-oxidative processes (E°'([MnCp*2]0*/-) = -0.18 V and E°'([ReCp*2]0*/-) = -0.20 V vs Fc+/0). These results showcase the rich electronic structure of low spin d5 metallocenes and their promise as excited state reductants.

Observation of parallel intersystem crossing and charge transfer-state dynamics in [Fe(bpy)3]2+ from ultrafast 2D electronic spectroscopy.

Transition metal-based charge-transfer complexes represent a broad class of inorganic compounds with diverse photochemical applications. Charge-transfer complexes based on earth-abundant elements have been of increasing interest, particularly the canonical [Fe(bpy)3]2+. Photoexcitation into the singlet metal-ligand charge transfer (1MLCT) state is followed by relaxation first to the ligand-field manifold and then to the ground state. While these dynamics have been well-studied, processes within the MLCT manifold that facilitate and/or compete with relaxation have been more elusive. We applied ultrafast two-dimensional electronic spectroscopy (2DES) to disentangle the dynamics immediately following MLCT excitation of this compound. First, dynamics ascribed to relaxation out of the initially formed 1MLCT state was found to correlate with the inertial response time of the solvent. Second, the additional dimension of the 2D spectra revealed a peak consistent with a ∼20 fs 1MLCT → 3MLCT intersystem crossing process. These two observations indicate that the complex simultaneously undergoes intersystem crossing and direct conversion to ligand-field state(s). Resolution of these parallel pathways in this prototypical earth-abundant complex highlights the ability of 2DES to deconvolve the otherwise obscured excited-state dynamics of charge-transfer complexes.

Ferrous and ferric complexes with cyclometalating N-heterocyclic carbene ligands: a case of dual emission revisited.

Iron N-heterocyclic carbene (FeNHC) complexes with long-lived charge transfer states are emerging as a promising class of photoactive materials. We have synthesized [FeII(ImP)2] (ImP = bis(2,6-bis(3-methylimidazol-2-ylidene-1-yl)phenylene)) that combines carbene ligands with cyclometalation for additionally improved ligand field strength. The 9 ps lifetime of its 3MLCT (metal-to-ligand charge transfer) state however reveals no benefit from cyclometalation compared to Fe(ii) complexes with NHC/pyridine or pure NHC ligand sets. In acetonitrile solution, the Fe(ii) complex forms a photoproduct that features emission characteristics (450 nm, 5.1 ns) that were previously attributed to a higher (2MLCT) state of its Fe(iii) analogue [FeIII(ImP)2]+, which led to a claim of dual (MLCT and LMCT) emission. Revisiting the photophysics of [FeIII(ImP)2]+, we confirmed however that higher (2MLCT) states of [FeIII(ImP)2]+ are short-lived (<10 ps) and therefore, in contrast to the previous interpretation, cannot give rise to emission on the nanosecond timescale. Accordingly, pristine [FeIII(ImP)2]+ prepared by us only shows red emission from its lower 2LMCT state (740 nm, 240 ps). The long-lived, higher energy emission previously reported for [FeIII(ImP)2]+ is instead attributed to an impurity, most probably a photoproduct of the Fe(ii) precursor. The previously reported emission quenching on the nanosecond time scale hence does not support any excited state reactivity of [FeIII(ImP)2]+ itself.

Probing the effect of nitro-substituents in the modulation of LUMO energies for directional electron transport through 4d6 ruthenium(II)-based metallosurfactants.

Electron-withdrawing nitro-substituents were installed onto terpyridine- and phenanthroline-based metallosurfactants with 4d6 ruthenium(II), which were deposited as Langmuir-Blodgett monolayers aiming to study the feasibility of charge transport in Au|LB|Au junctions. The nitro groups are intended to modulate the energy of the frontier molecular orbitals to near to, or match that of Fermi levels in the gold electrodes. A series of heteroleptic metallosurfactants [RuII(C18OPh-terpy)(X-terpy)](PF6)2 and [RuII(C18OPh-terpy)(X-phen)Cl]PF6 were synthesized, where C18OPh-terpy is the 4'-[4-(octadecyloxy)phenyl]-2,2':6',2''-terpyridine amphiphile common to all species, X-terpy is a terpyridine with-H (1) or-phenyl-NO2 (2) and X-phen is a phenanthroline with-H (3) or-NO2 (4) groups. These metallosurfactants were characterized by experimental and computational methods, and the presence of nitro groups affect more affordable reductions at less negative potentials, as well as slightly more positive oxidations, these changes are less pronounced in species 2 than in 4. Species 1 and 2 showed limited Pockels-Langmuir and Langmuir-Blodgett film formation with lower collapse pressure of 27 mN m-1. In contrast, metallosurfactants 3 and 4 showed enhanced hydrophilicity indicated by higher collapse pressures of ca. 36 mN m-1. The LB monolayers of 3 and 4 were deposited on gold electrodes to form Au|LB|Au junctions and electron transport was measured as I/V curves. The NO2-bearing species 4 showed asymmetric curves associated with directional electron transport with amplitudes up to -2.0 nA and rectification ratios from 5 to 26 between -1 to +1 V and from 3 to 14 between -3 to +3 V.

Lewis Acids and Electron-Withdrawing Ligands Accelerate CO Coordination to Dinuclear CuI Compounds.

A series of dinuclear molecular copper complexes were prepared and used to model the binding and Lewis acid stabilization of CO in heterogeneous copper CO2 reduction electrocatalysts. Experimental studies (including measurement of rate and equilibrium constants) and electronic structure calculations suggest that the key kinetic barrier for CO binding may be a σ-interaction between CuI and the incoming CO ligand. The rate of CO coordination can be increased upon the addition of Lewis acids or electron-withdrawing substituents on the ligand backbone. Conversely, Keq for CO coordination can be increased by adding electron density to the metal centers of the compound, consistent with stronger π-backbonding. Finally, the electrochemically measured kinetic results were mapped onto an electrochemical zone diagram to illustrate how these system changes enabled access to each zone.

Isocyanide Ligands Promote Ligand-to-Metal Charge Transfer Excited States in a Rhenium(II) Complex.

A metal-to-ligand charge transfer with mixed intraligand character is observed for the rhenium hexakisarylisocyanide complex [Re(CNAr)6]PF6 (CNAr = 2,6-dimethylphenylisocyanide, λmax = 300 nm). Upon oxidation to [Re(CNAr)6](PF6)2, the dominant low energy optical transition is a ligand-to-metal charge transfer (LMCT) mixed with intraligand transitions (λmax = 650 nm). TD-DFT was used to identify the participating ligand-based orbitals in the LMCT transition, revealing that the majority of the donor orbital is based on the aryl ring (85%) as opposed to the CN bond (14%). For both [Re(CNAr)6]+ and [Re(CNAr)6]2+, structural characterization by X-ray diffraction reveals deviations from Oh geometry at the central Re ion, with larger reduction in symmetry observed for Re(II). For [Re(CNAr)6]+, these structural changes lead to a broadening of the strong ν(C≡N) stretch (2065 cm-1), as the degeneracy of the T1u IR-active mode is broken. Furthermore, a shoulder is observed for this ν(C≡N) stretch, resulting from deviation of the C-N-Ar bond from linearity. By contrast, [Re(CNAr)6]2+ has two weak bands in the ν(C≡N) region (2065 and 2121 cm-1). DFT calculations indicate that reduction of symmetry at the central rhenium ion manifests in the decrease in intensity and the observed split of the ν(C≡N) band. Stability of both complexes are limited by light-induced decomposition where Re(I) dissociates a isocyanide ligand upon irradiation and Re(II) absorbance decays under ambient light. These data provide new insights to the electronic structure of [Re(CNAr)6]2+, enhancing our understanding of LMCT excited states and the versatility of isocyanide ligands.

Extended π-Conjugated Ligands Tune Excited-State Energies of Iron(II) Polypyridine Dyes.

Over the past decade, iron(II) polypyridines have gained a lot of attention as potential chromophores and sensitizers due to the low cost and high abundance of iron. Unfortunately, most iron(II) polypyridines are poor chromophores since their initially excited, photoactive metal-to-ligand charge transfer (MLCT) states quickly decay into non-photoactive metal-centered (MC) states. Many strategies to increase their lifetime have been pursued, built mainly around increasing the ligand field strength of these complexes and thus destabilizing the MC states. In this work, we aim to design a new class of Fe(II) complexes by stabilizing the energies of their MLCT states. To this end, we employ density functional theory (DFT) and time-dependent DFT to investigate a series of Fe(II) complexes, [Fe(L/X)2,4(N^N)]2+/2- where L/X represents either cyanide, isocyanide, or bipyridine ligands and N̂N stands for bidentate-extended π-conjugated ligands derived from the bipyridine. The L/X ligands tune the energetics of the Fe-based t2g molecular orbitals, while the amount of π-conjugation on the N^N ligand impacts the energies of its π and π* orbitals, thus tuning the energetics of the MLCT and the ligand-centered (LC) states. Overall, our results suggest that the use of N^N ligands with the extended π-conjugation is a viable strategy to tune the relative energies of MLCT, LC, and MC states.

Manipulating Excited State Properties of Iridium Phenylpyridine Complexes with "Push-Pull" Substituents.

We have prepared a series of complexes of the type [IrIII(ppy)2(L]n+ complexes (1-4), where ppy is a substituted 2-phenylpyridine and L is a chelating phosphine thioether ligand. The parent complex (1) comprises an unsubstituted phenylpyridine ligand, whereas complex 2 contains a nitro substituent on the pyridine ring, complex 3 features a diphenylamine group on the phenyl ring, and 4 has both nitro and diphenylamine groups. Crystallographic, 1H NMR, and elemental analysis data are consistent with each of the chemical formulae. DFT (density functional theory) computational results show a complicated electronic structure with contributions from Ir, ppy, and the PS ligand. Ultrafast pump-probe data show strong contributions from the phenylpyridine moieties as well as strong panchromatic excited state absorption transitions. The data show that nitro and/or diphenylamine substituents dominate the spectroscopy of this series of compounds.

A Spectroscopically Observed Iron Nitrosyl Intermediate in the Reduction of Nitrate by a Surface-Conjugated Electrocatalyst.

We report an iron-based graphite-conjugated electrocatalyst (GCC-FeDIM) that combines the well-defined nature of homogeneous molecular electrocatalysts with the robustness of a heterogeneous electrode. A suite of spectroscopic methods, supported by the results of DFT calculations, reveals that the electrode surface is functionalized by high spin (S = 5/2) Fe(III) ions in an FeN4Cl2 coordination environment. The chloride ions are hydrolyzed in aqueous solution, with the resulting cyclic voltammogram revealing a Gaussian-shaped wave assigned to 1H+/1e- reduction of surface Fe(III)-OH surface. A catalytic wave is observed in the presence of NO3-, with an onset potential of -1.1 V vs SCE. At pH 6.0, GCC-FeDIM rapidly reduces NO3- to ammonium and nitrite with 88 and 6% Faradaic efficiency, respectively. Mechanistic studies, including in situ X-ray absorption spectroscopy, suggest that electrocatalytic NO3- reduction involves an iron nitrosyl intermediate. The Fe-N bond length (1.65 Å) is similar to that observed in {Fe(NO)}6 complexes, which is supported by the results of DFT calculations.

Buffer Assists Electrocatalytic Nitrite Reduction by a Cobalt Macrocycle Complex.

This work reports a combined experimental and computational study of the activation of an otherwise catalytically inactive cobalt complex, [Co(TIM)Br2]+, for aqueous nitrite reduction. The presence of phosphate buffer leads to efficient electrocatalysis, with rapid reduction to ammonium occurring close to the thermodynamic potential and with high Faradaic efficiency. At neutral pH, increasing buffer concentrations increase catalytic current while simultaneously decreasing overpotential, although high concentrations have an inhibitory effect. Controlled potential electrolysis and rotating ring-disk electrode experiments indicate that ammonium is directly produced from nitrite by [Co(TIM)Br2]+, along with hydroxylamine. Mechanistic investigations implicate a vital role for the phosphate buffer, specifically as a proton shuttle, although high buffer concentrations inhibit catalysis. These results indicate a role for buffer in the design of electrocatalysts for nitrogen oxide conversion.

Electron transport through a (terpyridine)ruthenium metallo-surfactant containing a redox-active aminocatechol derivative.

Aiming to develop a new class of metallosurfactants with unidirectional electron transfer properties, a (terpyridine) ruthenium complex containing a semiquinone derivative L2, namely [RuIII(Lterpy)(L2)Cl]PF6 (1), was synthesized and structurally characterized as a solid and in solution. The electronic and redox behaviour of 1 was studied experimentally as well as by means of DFT methods, and is indicative of significant orbital mixing and overlap between metal and ligands. The complex forms stable Pockels-Langmuir films at the air-water interface and allows for the formation of thin films onto gold electrodes to prepare nanoscale Au|LB 1|Au junctions for current-voltage (I/V) analysis. Complex 1 shows asymmetric electron transfer with a maximum rectification ratio of 32 based on tunnelling through MOs of the aminocatechol derivative.

The ligand-to-metal charge transfer excited state of [Re(dmpe)3]2.

The ligand-to-metal charge transfer (LMCT) transitions of [Re(dmpe)3]2+ (dmpe = bis-1,2-(dimethylphosphino)ethane) were interrogated using UV/Vis absorbance spectroscopy, photoluminescence spectroscopy, and time-dependent density functional theory. The solvent dependence of the lowest energy charge transfer transition was quantified; no solvatochromism was observed. TD-DFT calculations reveal the dominant LMCT transition is highly symmetric and delocalized involving all phopshine ligand donors in the charge transfer, providing an understanding for the absence of solvatochromism of [Re(dmpe)3]2+.

Interpolation Methods for Molecular Potential Energy Surface Construction.

The concept of a potential energy surface (PES) is one of the most important concepts in modern chemistry. A PES represents the relationship between the chemical system's energy and its geometry (i.e., atom positions) and can provide useful information about the system's chemical properties and reactivity. Construction of accurate PESs with high-level theoretical methodologies, such as density functional theory, is still challenging due to a steep increase in the computational cost with the increase of the system size. Thus, over the past few decades, many different mathematical approaches have been applied to the problem of the cost-efficient PES construction. This article serves as a short overview of interpolative methods for the PES construction, including global polynomial interpolation, trigonometric interpolation, modified Shepard interpolation, interpolative moving least-squares, and the automated PES construction derived from these.

Halogenation affects driving forces, reorganization energies and "rocking" motions in strained [Fe(tpy)2]2+ complexes.

Controlling the energetics of spin crossover (SCO) in Fe(II)-polypyridine complexes is critical for designing new multifunctional materials or tuning the excited-state lifetimes of iron-based photosensitizers. It is well established that the Fe-N "breathing" mode is important for intersystem crossing from the singlet to the quintet state, but this does not preclude other, less obvious, structural distortions from affecting SCO. Previous work has shown that halogenation at the 6 and 6'' positions of tpy (tpy = 2,2';6',2''-terpyridine) in [Fe(tpy)2]2+ dramatically increased the lifetime of the excited MLCT state and also had a large impact on the ground state spin-state energetics. To gain insight into the origins of these effects, we used density functional theory calculations to explore how halogenation impacts spin-state energetics and molecular structure in this system. Based on previous work we focused on the ligand "rocking" motion associated with SCO in [Fe(tpy)2]2+ by constructing one-dimensional potential energy surfaces (PESs) along the tpy rocking angle for various spin states. It was found that halogenation has a clear and predictable impact on ligand rocking and spin-state energetics. The rocking is correlated to numerous other geometrical distortions, all of which likely affect the reorganization energies for spin-state changes. We have quantified trends in reorganization energy and also driving force for various spin-state changes and used them to interpret the experimentally measured excited-state lifetimes.

Are all charge-transfer parameters created equally? A study of functional dependence and excited-state charge-transfer quantification across two dye families.

Small molecule organic dyes have many potential uses in medicine, textiles, forensics, and light-harvesting technology. Being able to computationally predict the spectroscopic properties of these dyes could greatly expedite screening efforts, saving time and materials. Time-dependent density functional theory (TD-DFT) has been shown to be a good tool for this in many instances, but characterizing electronic excitations with charge-transfer (CT) character has historically been challenging and can be highly sensitive to the chosen exchange-correlation functional. Here we present a combined experimental and computational study of the excited-state electronic structure of twenty organic dyes obtained from the Max Weaver Dye Library at NCSU. Results of UV-vis spectra calculations on these dyes with six different exchange-correlation functionals, BP86, B3LYP, PBE0, M06, BH and HLYP, and CAM-B3LYP, were compared against their measured UV-vis spectra. It was found that hybrid functionals with modest amounts (20-30%) of included Hartree-Fock exchange are the most effective at matching the experimentally determined λmax. The interplay between the observed error, the functional chosen, and the degree of CT was analyzed by quantifying the CT character of λmax using four orbital and density-based metrics, Λ, Δr, SC and DCT, as well as the change in the dipole moment, Δµ. The results showed that the relationship between CT character and the functional dependence of error is not straightforward, with the observed behavior being dependent both on how CT was quantified and the functional groups present in the molecules themselves. It is concluded that this may be a result of the examined excitations having intermediate CT character. Ultimately it was found that the nature of the molecular "family" influenced how a given functional behaved as a function of CT character, with only two of the examined CT quantification methods, Δr and DCT, showing consistent behavior between the different molecular families. This suggests that further work needs to be done to ensure that currently used CT quantification methods show the same general trends across large sets of multiple dye families.

Reduced-dimensional surface hopping with offline-online computations.

Molecular dynamics simulations often classically evolve the nuclear geometry on adiabatic potential energy surfaces (PESs), punctuated by random hops between energy levels in regions of strong coupling, in an algorithm known as surface hopping. However, the computational expense of integrating the geometry on a full-dimensional PES and computing the required couplings can quickly become prohibitive as the number of atoms increases. In this work, we describe a method for surface hopping that uses only important reaction coordinates, performs all expensive evaluations of the true PESs and couplings only once before simulating dynamics (offline), and then queries the stored values during the surface hopping simulation (online). Our Python codes are freely available on GitHub. Using photodissociation of azomethane as a test case, this method is able to reproduce experimental results that have thus far eluded ab initio surface hopping studies.

Electrocatalytic nitrate reduction with Co-based catalysts: comparison of DIM, TIM and cyclam ligands.

Over the past century, the global concentration of environmental nitrate has increased significantly from human activity, which has resulted in the contamination of drinking water and aquatic hypoxia around the world, so the development of effective nitrate-reducing agents is urgent. This work compares three potential macrocycle-based nitrate reduction electrocatalysts: [Co(DIM)]3+, [Co(cyclam)]3+ and [Co(TIM)]3+. Although all three complexes have similar structures, only [Co(DIM)]3+ has been experimentally determined to be an active electrocatalyst for selective nitrate reduction to produce ammonia in water. While [Co(cyclam)]3+ can reduce aqueous nitrate to ammonia and hydroxylamine at heavy metal electrodes, [Co(TIM)]3+ is inactive for the reduction of nitrate. As an initial step to understanding what structural and electronic properties are important for efficient electrocatalysts for nitrate reduction, density functional theory (DFT) was employed to investigate the electronic structure of the three Co complexes, with the reduction potentials calibrated to experimental results. Moreover, DFT was employed to explore four different reaction mechanisms for the first steps of nitrate reduction. The calculated reaction barriers reveal how a combination of electron transfer in a redox non-innocent complex, substrate binding, and intramolecular hydrogen bonding dictates the activity of Co-based catalysts toward nitrate reduction.

Efficient Approximation of Potential Energy Surfaces with Mixed-Basis Interpolation.

The potential energy surface (PES) describes the energy of a chemical system as a function of its geometry and is a fundamental concept in modern chemistry. A PES provides much useful information about the system, including the structures and energies of various stationary points, such as stable conformers (local minima) and transition states (first-order saddle points) connected by a minimum-energy path. Our group has previously produced surrogate reduced-dimensional PESs using sparse interpolation along chemically significant reaction coordinates, such as bond lengths, bond angles, and torsion angles. These surrogates used a single interpolation basis, either polynomials or trigonometric functions, in every dimension. However, relevant molecular dynamics (MD) simulations often involve some combination of both periodic and nonperiodic coordinates. Using a trigonometric basis on nonperiodic coordinates, such as bond lengths, leads to inaccuracies near the domain boundary. Conversely, polynomial interpolation on the periodic coordinates does not enforce the periodicity of the surrogate PES gradient, leading to nonconservation of total energy even in a microcanonical ensemble. In this work, we present an interpolation method that uses trigonometric interpolation on the periodic reaction coordinates and polynomial interpolation on the nonperiodic coordinates. We apply this method to MD simulations of possible isomerization pathways of azomethane between cis and trans conformers. This method is the only known interpolative method that appropriately conserves total energy in systems with both periodic and nonperiodic reaction coordinates. In addition, compared to all-polynomial interpolation, the mixed basis requires fewer electronic structure calculations to obtain a given level of accuracy, is an order of magnitude faster, and is freely available on GitHub.

Evidence for a lowest energy 3MLCT excited state in [Fe(tpy)(CN)3].

Transient absorption data of [FeII(tpy)(CN)3]- reveals spectroscopic signatures indicative of 3MLCT with a ∼10 ps kinetic component. These data are supported by DFT and TD-DFT calculations, which show that excited state ordering is responsive to the number of cyanide ligands on the complex.