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Although vibronic coupling phenomena have been recognized in the excite state dynamics of transition metal complexes, its impact on photoinduced electron transfer (PET) remains largely unexplored. This study investigates coherent wavepacket (CWP) dynamics during PET processes in a covalently linked electron donor-acceptor complex featuring a cyclometalated Pt(ii) dimer as the donor and naphthalene diimide (NDI) as the acceptors. Upon photoexciting the Pt(ii) dimer electron donor, ultrafast broadband transient absorption spectroscopy revealed direct modulation of NDI radical anion formation through certain CWP motions and correlated temporal evolutions of the amplitudes for these CWPs with the NDI radical anion formation. These results provide clear evidence that the CWP motions are the vibronic coherences coupled to the PET reaction coordinates. Normal mode analysis identified that the CWP motions originate from vibrational modes associated with the dihedral angles and bond lengths between the planes of the cyclometalating ligand and the NDI, the key modes altering their π-interaction, consequently influencing PET dynamics. The findings highlight the pivotal role of vibrations in shaping the favorable trajectories for the efficient PET processes.
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Chemical transformations in charge transfer states result from the interplay between electronic dynamics and nuclear reorganization along excited-state trajectories. Here, we investigate the ultrafast structural dynamics following photoinduced electron transfer from the metal-metal-to-ligand charge transfer state of an electron donor, a Pt dimer complex, to a covalently linked electron acceptor group using ultrafast time-resolved wide-angle X-ray scattering and optical transient absorption spectroscopy methods to disentangle the interdependence of the excited-state electronic and nuclear dynamics. Following photoexcitation, Pt-Pt bond formation and contraction takes up to 1 ps, much slower than the corresponding process in analogous complexes without electron acceptor groups. Because the Pt-Pt distance change is slow with respect to excited-state electron transfer, it can affect the rate of electron transfer. These results have potential impacts on controlling electron transfer rates via structural alterations to the electron donor group, tuning the charge transfer driving force.
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Photoexcited molecular trajectories on potential energy surfaces (PESs) prior to thermalization are intimately connected to the photochemical reaction outcome. The excited-state trajectories of a diplatinum complex featuring photo-activated metal-metal σ-bond formation and associated Pt-Pt stretching motions were detected in real time using femtosecond wide-angle X-ray solution scattering. The observed motions correspond well with coherent vibrational wavepacket motions detected by femtosecond optical transient absorption. Two key coordinates for intersystem crossing have been identified, the Pt-Pt bond length and the orientation of the ligands coordinated with the platinum centers, along which the excited-state trajectories can be projected onto the calculated PESs of the excited states. This investigation has gleaned novel insight into electronic transitions occurring on the time scales of vibrational motions measured in real time, revealing ultrafast nonadiabatic or non-equilibrium processes along excited-state trajectories involving multiple excited-state PESs.
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Two-coordinate transition metal complexes are exciting candidates for single-molecule magnets (SMMs) because their highly axial coordination environments lead to sizeable magnetic anisotropy. We report a series of five structurally related two-coordinate Fe(II) m-terphenyl complexes (4-R-2,6-Xyl2C6H2)2Fe [R = tBu (1), SiMe3 (2), H (3), Cl (4), CF3 (5)] where, by changing the functionalisation of the para-substituent (R), we alter their magnetic function. All five complexes are field-induced single-molecule magnets, with relaxation rates that are well-described by a combination of direct and Raman mechanisms. By using more electron donating R groups we were able to slow the rate of magnetic relaxation. Our ab initio calculations predict a large crystal field splitting (>850 cm-1) and sizeable zero-field splitting parameters (ca. -60 cm-1, |E| < 0.2 cm-1) for 1-5. These favourable magnetic properties suggest that m-terphenyl ligands have untapped potential as chemically versatile ligands able to impose highly axial crystal fields.
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The effects of para-substitution on the structural and electronic properties of four series of two-coordinate m-terphenyl Group 12 complexes (R-Ar#)2M (M = Zn, Cd, Hg; R = t-Bu 1-3, SiMe3 4-6, Cl 7-9, CF3 10-12, where R-Ar# = 2,6-{2,6-Xyl}2-4-R-C6H2 and 2,6-Xyl = 2,6-Me2C6H3) have been investigated. X-ray crystallography shows little structural variation across the series, with no significant change in the C-M-C bond distances and angles. However, considerable electronic differences are revealed by heteronuclear nuclear magnetic resonance (NMR) spectroscopy; a linear correlation is observed between the 113Cd, 199Hg, and 1H (2,6-Xyl methyl protons) NMR chemical shifts of the para-substituted complexes and the Hammett constants for the R-substituents. Specifically, an upfield shift in the NMR signal is observed with increasingly electron-withdrawing R-substituents. Density functional theory (DFT) calculations are employed to attempt to rationalize these trends.
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Proton-coupled electron transfer (PCET) was studied for the ground and excited electronic states of a [Ru(terpy)(bpm)(OH2)(PF6)2] complex, Ru-bpm. Cyclic voltammetry measurements show that the Ru(II)-aqua moiety undergoes PCET to form a Ru(IV)-oxo moiety in the anodic region, while the bpm ligand undergoes PCET to form bpmH2 in the cathodic region. The photophysical behavior of Ru-bpm was studied using steady-state and femtosecond transient UV-vis absorption spectroscopy, coupled with density functional theory (DFT) calculations. The lowest-lying excited state of Ru-bpm is described as a (Ru â bpm) metal-to-ligand charge-transfer (MLCT) state, while the metal-centered (MC) excited state was found computationally to be close in energy to the lowest-energy bright MLCT state (MC state was 0.16 eV above the MLCT state). The excited-state kinetics of Ru-bpm were found via transient absorption spectroscopy to be short-lived and were fit well to a biexponential function with lifetimes τ1 = 4 ps and τ2 = 65 ps in aqueous solution. Kinetic isotope effects of 1.75 (τ1) and 1.61 (τ2) were observed for both decay components, indicating that the solvent plays an important role in the excited-state dynamics of Ru-bpm. Based on the pH-dependent studies and the results from prior studies of similar Ru-complexes, we hypothesize that the 3MLCT state forms an excited-state hydrogen-bond adduct with the solvent molecules and that this process occurs with a 4 ps lifetime. The formation of such a hydrogen-bond complex is consistent with the electronic density accumulation at the peripheral N atoms of the bpm moiety in the 3MLCT state. The hydrogen-bonded state 3MLCT decays to the ground state with a 65 ps lifetime. Such a short lifetime is likely associated with the efficient vibrational energy transfer from the 3MLCT state to the solvent.
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Rutenio , Electrónica , Electrones , Ligandos , Protones , Rutenio/química , SolventesRESUMEN
Ultrafast excited state processes of transition metal complexes (TMCs) are governed by complicated interplays between electronic and nuclear dynamics, which demand a detailed understanding to achieve optimal functionalities of photoactive TMC-based materials for many applications. In this work, we investigated a cyclometalated platinum(II) dimer known to undergo a Pt-Pt bond contraction in the metal-metal-to-ligand-charge-transfer (MMLCT) excited state using femtosecond broadband transient absorption (fs-BBTA) spectroscopy in combination with geometry optimization and normal mode calculations. Using a sub-20 fs pump and broadband probe pulses in fs-BBTA spectroscopy, we were able to correlate the coherent vibrational wavepacket (CVWP) evolution with the stimulated emission (SE) dynamics of the 1MMLCT state. The results demonstrated that the 145 cm-1 CVWP motions with the damping times of â¼0.9 ps and â¼2 ps originate from coherent Pt-Pt stretching vibrations in the singlet and triplet MMLCT states, respectively. On the basis of excited state potential energy surface calculations in our previous work, we rationalized that the CVWP transfer from the Franck-Condon (FC) state to the 3MMLCT state was mediated by a triplet ligand-centered (3LC) intermediate state through two step intersystem crossing (ISC) on a time scale shorter than a period of the Pt-Pt stretching wavepacket motions. Moreover, it was found that the CVWP motion had 110 cm-1 frequency decays with the damping time of â¼0.2 ps, matching the time constant of 0.253 ps, corresponding to a redshift in the SE feature at early times. This observation indicates that the Pt-Pt bond contraction changes the stretching frequency from 110 to 145 cm-1 and stabilizes the 1MMLCT state relative to the 3LC state with a â¼0.2 ps time scale. Thus, the ultrafast ISC from the 1MMLCT to the 3LC states occurs before the Pt-Pt bond shortening. The findings herein provide insight into understanding the impact of Pt-Pt bond contraction on the ultrafast branching of the 1MMLCT population into the direct (1MMLCT â 3MMLCT) and indirect ISC pathways (1MMLCT â 3LC â 3MMLCT) in the Pt(II) dimer. These results revealed intricate excited state electronic and nuclear motions that could steer the reaction pathways with a level of detail that has not been achieved before.
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Complejos de Coordinación , Vibración , Ligandos , Platino (Metal)/química , Teoría CuánticaRESUMEN
In photosynthetic systems employing multiple transition metal centers, the properties of charge-transfer states are tuned by the coupling between metal centers. Here, we use ultrafast optical and X-ray spectroscopies to elucidate the effects of metal-metal interactions in a bimetallic tetrapyridophenazine-bridged Os(ii)/Cu(i) complex. Despite having an appropriate driving force for Os-to-Cu hole transfer in the Os(ii) moiety excited state, no such charge transfer was observed. However, excited-state coupling between the metal centers is present, evidenced by variations in the Os MLCT lifetime depending on the identity of the opposite metal center. This coupling results in concerted coherent vibrations appearing in the relaxation kinetics of the MLCT states for both Cu and Os centers. These vibrations are dominated by metal-ligand contraction at the Cu/Os centers, which are in-phase and linked through the conjugated bridging ligand. This study shows how vibronic coupling between transition metal centers affects the ultrafast dynamics in bridged, multi-metallic systems from the earliest times after photoexcitation to excited-state decay, presenting avenues for tuning charge-transfer states through judicious choice of metal/ligand groups.
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Intersystem crossing (ISC), a vital component of the electronic and nuclear transitions that compose photophysics, has been successfully simulated in light elements and transition metal complexes. Derived from the Z-dependent spin-orbit coupling (SOC), ISC is expected to be of greater importance in heavier elements, but few attempts have been made at the simulation of ISC in lanthanides or actinides. In this work, we explore several of the challenges that will need to be overcome in order to treat ISC in late-row elements, including the loss of spin as a good quantum number, the need to include SOC variationally via two- or four-component electronic structure, and the high density of states present in late-row complexes. Density functional theory (DFT) calculations are used to illustrate several of these effects, while a model Hamiltonian is used to illustrate the importance of momentum rescaling in surface hopping simulations of strongly coupled states.
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Teoría Cuántica , Elementos de TransiciónRESUMEN
High-energy X-ray scattering and pair distribution function analysis (HEXS/PDF) is a powerful method to reveal the structure of materials lacking long-range order, but is underutilized for molecular complexes in solution. We demonstrate the application of HEXS/PDF with 0.26â Å resolution to uncover the solution structure of five bimetallic CuI /RuII /OsII complexes. HEXS/PDF of each complex in acetonitrile solution confirms the pairwise distances in the local coordination sphere of each metal center as well as the metalâ â â metal distances separated by over 12â Å. The metalâ â â metal distance detected in solution is compared with that from the crystal structure and molecular models to confirm that distortions to the metal bridging ligand are unique to the solid state. This work presents the first example of observing sub-Ångström conformational differences by direct comparison of solution phase and solid-state structures and shows the potential for HEXS/PDF in the determination of solution structure of single molecules.
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A series of platinum(II) bimetallic complexes were studied to investigate the effects of ligands on both the geometric and electronic structure. Modulating the Pt-Pt distance through the bridging ligand architecture was found to dictate the nature of the lowest energy electronic transitions, localized in one-half of the molecule or delocalized across the entire molecule. By reducing the separation between the platinum atoms, the lowest energy electronic transitions will be dominated by the metal-metal-to-ligand charge transfer transition. Conversely, by increasing the distance between the platinum atoms, the lowest electronic transition will be largely localized metal-to-ligand charge transfer or ligand centered in nature. Additionally, the cyclometalating ligands were observed to have a noticeable stabilizing effect on the triplet excited states as the conjugation increased, arising from geometric reorientation and increased electron delocalization of the ligands. Such stabilization of the triplet state energy has been shown to alter the excited state potential energy landscape as well as the excited state trajectory.
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Intricate potential energy surfaces (PESs) of some transition metal complexes (TMCs) pose challenges in mapping out initial excited-state pathways that could influence photochemical outcomes. Ultrafast intersystem crossing (ISC) dynamics of four structurally related platinum(II) dimer complexes were examined by detecting their coherent vibrational wavepacket (CVWP) motions of Pt-Pt stretching mode in the metal-metal-to-ligand-charge-transfer excited states. Structurally dependent CVWP behaviors (frequency, dephasing time, and oscillation amplitudes) were captured by femtosecond transient absorption spectroscopy, analyzed by short-time Fourier transformation, and rationalized by quantum mechanical calculations, revealing dual ISC pathways. The results suggest that the ligands could fine-tune the PESs to influence the proximity of the conical intersections of the excited states with the Franck-Condon state and thus to control the branching ratio of the dual ISC pathways. This comparative study presents future opportunities in control excited-state trajectories of TMCs via ligand structures.
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The effect of para-substitution upon the structural and electronic properties of a series of m-terphenyl lithium complexes [R-Ar#-Li]2 (R = t-Bu 1, SiMe32, H 3, Cl 4, CF35; where R-Ar# = 2,6-{2,6-Xyl}2-4-R-C6H2 and 2,6-Xyl = 2,6-Me2C6H3) has been investigated. X-ray crystallography reveals the complexes to be structurally similar, with little variation in C-M-C bond lengths and angles across the series. However, in-depth NMR spectroscopic studies reveal notable electronic differences, showing a linear correlation between the 7Li{1H} NMR chemical shifts of the para-substituted complexes and their Hammett constants. The flanking methyl protons exhibit a similar electronic shift in the 1H NMR spectra, which has been rationalised by the presence of through-space LiH interactions, as evidenced by two-dimensional 7Li-1H heteronuclear Overhauser spectroscopy (HOESY). In both cases, electron-withdrawing substituents are found to cause an upfield peak shift. A computational analysis is employed to account for these trends.
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We report a study of chromophore-catalyst assemblies composed of light harvesting hexabenzocoronene (HBC) chromophores axially coordinated to two cobaloxime complexes. The chromophore-catalyst assemblies were prepared using bottom-up synthetic methodology and characterized using solid-state NMR, IR, and x-ray absorption spectroscopy. Detailed steady-state and time-resolved laser spectroscopy was utilized to identify the photophysical properties of the assemblies, coupled with time-dependent DFT calculations to characterize the relevant excited states. The HBC chromophores tend to assemble into aggregates that exhibit high exciton diffusion length (D = 18.5 molecule2/ps), indicating that over 50 chromophores can be sampled within their excited state lifetime. We find that the axial coordination of cobaloximes leads to a significant reduction in the excited state lifetime of the HBC moiety, and this finding was discussed in terms of possible electron and energy transfer pathways. By comparing the experimental quenching rate constant (1.0 × 109 s-1) with the rate constant estimates for Marcus electron transfer (5.7 × 108 s-1) and Förster/Dexter energy transfers (8.1 × 106 s-1 and 1.0 × 1010 s-1), we conclude that both Dexter energy and Marcus electron transfer process are possible deactivation pathways in CoQD-A. No charge transfer or energy transfer intermediate was detected in transient absorption spectroscopy, indicating fast, subpicosecond return to the ground state. These results provide important insights into the factors that control the photophysical properties of photocatalytic chromophore-catalyst assemblies.
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The reaction between a two-coordinate Co(ii) diaryl complex and "GaI" affords 2,6-Pmp2C6H3CoGa3I5, in a new geometry for a heavier group 13-transition metal cluster. Experimental and computational investigations show that this compound is best described as a nido metalla-group 13 cluster.
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Exciton size and dynamics were studied in assemblies of two well-defined graphene quantum dots of varying size: hexabenzocoronene (HBC), where the aromatic core consists of 42 C atoms, and carbon quantum dot (CQD) with 78 C atoms. The synthesis of HBC and CQD were achieved using bottom-up chemical methods, while their assembly was studied using steady-state UV/vis spectroscopy, X-ray scattering, and electron microscopy. While HBC forms long ordered fibers, CQD was found not to assemble well. The exciton size and dynamics were studied using time-resolved laser spectroscopy. At early times (â¼100 fs), the exciton was found to delocalize over â¼1-2 molecular units in both assemblies, which reflects the confined nature of excitons in carbon-based materials and is consistent with the calculated value of â¼2 molecular units. Exciton-exciton annihilation measurements provided the exciton diffusion lengths of 16 and 3 nm for HBC and CQD, respectively.
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Bimetallic platinum complexes have interesting luminescent properties and feature long-lasting vibrational coherence and ultrafast intersystem crossing (ISC) after photoexcitation. Ultrafast triplet formation is driven by very strong spin-orbit coupling in these platinum (II) systems, where relativistic theoretical approaches beyond first-order perturbation theory are desirable. Using a fully variational relativistic theoretical method recently developed by the authors, we investigate the origins of ultrafast ISC in the [Pt(ppy) (µ-tBu2pz)]2 complex (ppy = phenylpyridine, pz = pyrazolate). Spin-orbit coupling values, evaluated along a Born-Oppenheimer molecular dynamics trajectory, are used to propagate electronic populations in time. Using this technique, we estimate ultrafast ISC rates of 15-134 fs in this species for the possible ISC pathways into the three low-lying triplet states.
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The change in electronic state from one spin multiplicity to another, known as intersystem crossing, occurs in molecules via the relativistic phenomenon of spin-orbit coupling. Current means of estimating intersystem crossing rates rely on the perturbative evaluation of spin-orbit coupling effects. This perturbative approach, valid in lighter atoms where spin-orbit coupling is weaker, is expected to break down for heavier elements where relativistic effects become dominant. Methods which incorporate spin-orbit effects variationally, such as the exact-two-component (X2C) method, will be necessary to treat this strong-coupling regime. We present a novel procedure which produces a diabatic basis of spin-pure electronic states coupled by spin-orbit terms, generated from fully variational relativistic calculations. This method is implemented within X2C using time-dependent density-functional theory and is compared to results from a perturbative relativistic study in the weak spin-orbit coupling regime. Additional calculations on a more strongly spin-orbit-coupled [UO2Cl4]2- complex further illustrate the strengths of this method. This procedure will be valuable in the estimation of intersystem crossing rates within strongly spin-coupled species.