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Polyyne bridges have attracted extensive interest as molecular wires due to their shallow distance dependence during charge transfer. Here, we investigate whether triplet energy transfer from cadmium selenide (CdSe) quantum dots (QDs) to anthracene acceptors benefits from the high conductance associated with polyyne bridges, especially from the potential cumulene character in their excited states. Introducing π-electron rich oligoyne bridges between the surface-bound anthracene-based transmitter ligands, we explore the triplet energy transfer rate between the CdSe QDs and anthracene core. Our femtosecond transient absorption results reveal that a rate constant damping coefficient of ß is 0.118 ± 0.011 Å-1, attributed to a through-bond coupling mechanism facilitated by conjugation among the anthracene core, the oligoyne bridges, and the COOâ anchoring group. In addition, oligoyne bridges lower the T1 energy level of the anthracene-based transmitters, enabling efficient triplet energy transfer from trapped excitons in CdSe QDs. Density-functional theory calculations suggest a slight cumulene character in these oligoyne bridges during triplet energy transfer, with diminished bond length alternation. This work demonstrates the potential of oligoyne bridges in mediating long-distance energy transfer.
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The structural factors affecting triplet-triplet annihilation (TTA) at the molecular level are not well-understood. Here, our steady-state photoluminescence and transient absorption results demonstrate that the spin statistical factor, η, decreases from 0.60 to 0.46 and 0.14 going from 9,10-diphenylanthracene (DPA) to the 1,5-DPA and 2,6-DPA isomers, respectively, during photon upconversion with a platinum octaethylporphyrin sensitizer. Density functional theory (DFT) shows that η depends on the energetics of hot triplet states and molecular rigidity. The significantly high conical intersection energy between the S0 and T1 states for 9,10-DPA gives its longer triplet lifetime. Time-dependent DFT calculations show that 9,10-DPA and 1,5-DPA can undergo high-level reverse intersystem crossing from their T2 and T3 states, respectively, to the bright S1 state, increasing the limit of the spin statistical factor. Both factors ultimately serve to enhance the TTA efficiency. This work provides insight into designing molecules for efficient light-emitting and photon upconversion applications.
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Two-dimensional covalent organic frameworks (2D-COFs) constitute an ideal platform for the design of novel optoelectronic materials. In this work, the donor-acceptor copolymer strategy for intramolecular singlet fission (iSF) is revisited and applied for the tailored design of a functional 2D-COF with iSF capabilities.
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Singlet fission (SF) is a two-step process in which a singlet splits into two triplets throughout the so-called correlated triplet-pair (1TT) state. Intramolecular SF (iSF) materials, in particular, have attracted growing interest as they can be easily implemented in single-junction solar cells and boost their power conversion efficiency. Still, the potential of iSF materials such as polymers and oligomers for photovoltaic applications has been partially hindered by their ability to go beyond the 1TT intermediate and generate free triplets, whose mechanism remains poorly understood. In this work, the main aspects governing the 1TT dissociation in donor-acceptor copolymers and the key features that optimize this process are exposed. First, we show that both thermodynamics and kinetics play a crucial role in the intramolecular triplet-pair separation and second, we uncover the inherent flexibility of the donor unit as the fundamental ingredient to optimize them simultaneously. Overall, these results provide a better understanding of the intramolecular 1TT dissociation process and establish a new paradigm for the development of novel iSF active materials.
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Singlet fission (SF) is a promising multiexciton-generating process. Its demanding energy splitting criterion - that the S1 energy must be at least twice that of T1 - has limited the range of materials capable of SF. We propose heteroatom oxidation as a robust strategy to achieve sufficient S1/T1 splitting, and demonstrate the potential of this approach for intramolecular SF.
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To identify the genesis of the differing magnetic behaviors for the ferro- (FO) and metamagnetic (MM) polymorphs of [FeCp*2][TCNQ] (Cp* = pentamethylcyclopentadienide; TCNQ = 7,7,8,8-tetracyano-p-quinodimethane) the low temperature (18 ± 1 K) structures of each polymorph were determined from high-resolution synchrotron powder diffraction data. Each polymorph possesses chains of alternating S = 1/2 [FeCp*2]Ë+ cations and S = 1/2 [TCNQ]Ë+, but with differing relative orientations. These as well as an additional paramagnetic polymorph do not thermally interconvert. In addition, the room and low (<70 ± 10 K) temperature structures of the MM polymorph, MMRT and MMLT, respectively, differ from that previously reported at 167 K (-106 °C) MM structure, and no evidence of either phase transition was previously noted even from the magnetic data. This transition temperature and enthalpy of this phase transition for MMRTâMM was determined to be 226.5 ± 0.4 K (-46.7 ± 0.4 °C) and 0.68 ± 0.04 kJ mol-1 upon warming, respectively, from differential calorimetry studies (DSC). All three MM phases are triclinic (P1[combining macron]) with the room temperature phase having a doubled unit cell relative to the other two. The lower temperature phase transition involves a small rearrangement of the molecular ions and shift in lattice parameters. These three MM and FO polymorphs have been characterized and form extended 1-D chains with alternating S = 1/2 [FeCp*2]Ë+ cations, and S = 1/2 [TCNQ]Ë- anions, whereas the fifth, paramagnetic (P) polymorph possesses S = 0 π-[TCNQ]22- dimers. At 18 ± 1 K the intrachain FeFe separations are 10.738(2) and 10.439(3) Å for the FO and MMLT polymorphs, respectively. The key structural differences between FO and MMLT at 18 ± 1 K are the 10% shorter interchain NN and the 2.8% shorter intrachain FeFe separation present for MMLT. Computational analysis of all nearest-neighbor spin couplings for the 18 K structures of FO and MMLT indicates that the intrachain [FeCp*2]Ë+[TCNQ]Ë- spin couplings (H = -2Si·Sj) are the strongest (4.95 and 6.5 cm-1 for FO and MMLT, respectively), as previously hypothesized, and are ferromagnetic due to their S = 1/2 spins residing in orthogonal orbitals. The change in relative [TCNQ]Ë-[TCNQ]Ë- orientations leads to a computed change from the ferromagnetic interaction (0.2 cm-1) for FO to an antiferromagnetic interaction (-0.1 cm-1) for MMLT in accord with its observed antiferromagnetic ground state. Hence, the magnetic ground state cannot be solely described by the dominant magnetic interactions.
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Donor-acceptor (D-A) copolymers have shown great potential for intramolecular singlet fission (iSF). Nonetheless, very few design principles exist for optimizing these systems for iSF, with very little knowledge about how to engineer them for this purpose. In recent work, a fundamental trade-off between the main electronic ingredients required for iSF capable D-A coplanar copolymers was revealed. Still, further investigations are needed to understand these limitations and learn how to bypass them. In this work, we propose to induce torsion as an effective way to circumvent the limits of the coplanar approach. We disclose the potential of noncoplanar copolymers with inherently low triplet energies that encompass all the characteristics required for iSF beyond the limiting values associated with fully coplanar systems. Our findings shed some light on the electronic structure aspects of D-A copolymers for iSF and offer a new avenue for the rational design of novel promising candidates.
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Mn(I) α-diimine carbonyl complexes have shown promise in the development of luminescent CO release materials (photoCORMs) for diagnostic and medical applications due to their ability to balance the energy of the low-lying metal-to-ligand charge transfer (MLCT) and metal-centered (MC) states. In this work, the excited state dynamics of [Mn(im)(CO)3(phen)]+ (im = imidazole; phen = 1,10-phenanthroline) is investigated by means of wavepacket propagation on the potential energy surfaces associated with the 11 low-lying Sn singlet excited states within a vibronic coupling model in a (quasi)-diabatic representation including 16 nuclear degrees of freedom. The results show that the early time photophysics (<400 fs) is controlled by the interaction between two MC dissociative states, namely, S5 and S11, with the lowest S1-S3 MLCT bound states. In particular, the presence of S1/S5 and S2/S11 crossings within the diabatic picture along the Mn-COaxial dissociative coordinate (qMn-COaxial) favors a two-stepwise population of the dissociative states, at about 60-70 fs (S11) and 160-180 fs (S5), which reaches about 10% within 200 fs. The one-dimensional reduced densities associated with the dissociative states along qMn-COaxial as a function of time clearly point to concurrent primary processes, namely, CO release vs entrapping into the S1 and S2 potential wells of the lowest luminescent MLCT states within 400 fs, characteristics of luminescent photoCORM.
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A strategy for enhancing the photocatalytic performance of MOF-based systems (MOF: metal-organic framework) is developed through the construction of MOF/MOF heterojunctions. The combination of MIL-167 with MIL-125-NH2 leads to the formation of MIL-167/MIL-125-NH2 heterojunctions with improved optoelectronic properties and efficient charge separation. MIL-167/MIL-125-NH2 outperforms its single components MIL-167 and MIL-125-NH2, in terms of photocatalytic H2 production (455 versus 0.8 and 51.2 µmol h-1 g-1, respectively), under visible-light irradiation, without the use of any cocatalysts. This is attributed to the appropriate band alignment of these MOFs, the enhanced visible-light absorption, and long charge separation within MIL-167/MIL-125-NH2. Our findings contribute to the discovery of novel MOF-based photocatalytic systems that can harvest solar energy and exhibit high catalytic activities in the absence of cocatalysts.
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Donor-acceptor (D-A) extended copolymers have shown great potential to be exploited for intramolecular singlet fission (iSF) because of their modular tunability and intrinsic ability to incorporate low-lying charge-transfer (CT) and a triplet-pair (1TT) states. While the SF mechanism has been widely debated in homo- and heterodimers, little is known about the singlet splitting process in A-D-A copolymer trimers. Unlike traditional two-site SF, the process of iSF in D-A copolymers involves three molecular units consisting of two A's and one D following an A-D-A polymeric chain. This scenario is, therefore, different from that of the homodimer analogues in terms of which states (if any) may drive the SF process. In this work, we identify how singlet splitting occurs in prototypical iSF D-A copolymer poly(benzodithiophene-alt-thiophene-1,1-dioxide) by means of wave packet propagations on the basis of the linear vibronic coupling model Hamiltonian. Our results reveal that three different mechanisms drive the S1 â 1TT population transfer via antisymmetric and symmetric vibrational motion, including two favorable mechanisms of direct and mediated interactions, as well as a parasitic decay pathway that potentially delays the process. Remarkably, we uncover the interplay between an upper state of marked multiexcitonic character and a low-lying CT state in balancing the splitting efficiency, which anticipates their major role in defining future guidelines for the molecular design of D-A copolymers for iSF.
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The vast chemical space of metal and ligand combinations in Transition Metal Complexes (TMCs) gives rise to a rich variety of electronic excited states with local and non-local character such as intra-ligand (IL), metal-centered (MC), metal-to-ligand (MLCT) or ligand-to-metal charge-transfer (LMCT) states. Those features are equally found in metal organic frameworks (MOFs), defined as modular materials built from metal-nodes connected through organic-ligands. Because of the electronic and structural complexity of MOFs, the computational description of their excited states is a formidable challenge for which two different approaches have been usually followed: the solid state and the molecular perspective. The first consists in analysing the frontier electronic bands and crystal orbitals of the electronic ground state (GS) in periodic boundary conditions, while the latter points to an accurate computation of the excited states in representative clusters at the molecular level. Herein, we apply both approaches to evaluate the optical absorption properties of three experimentally reported Ti(iv) mononuclear MOFs with in silico metal substitutions with Zn(ii), Cd(ii), Fe(ii), Ru(ii) and Zr(iv) ions, thus covering d10, d6 and d0 electronic configurations of 1st and 2nd row TMCs in MOFs. Our analysis captures the main electronic features attributed to these systems while we discuss the main advantages and drawbacks of both approximations.
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The thermal spin crossover (SCO) phenomenon refers to an entropy-driven spin transition in some materials based on d6-d9 transition metal complexes. While its molecular origin is well known, intricate SCO behaviours are increasingly common, in which the spin transition occurs concomitantly to e.g. phase transformations, solvent absorption/desorption, or order-disorder processes. The computational modelling of such cases is challenging, as it requires accurate spin state energies in the solid state. Density Functional Theory (DFT) is the best framework, but most DFT functionals are unable to balance the spin state energies. While a few hybrid functionals perform better, they are still too expensive for solid-state minima searches in moderate-size systems. The best alternative is to dress cheap local (LDA) or semi-local (GGA) DFT functionals with a Hubbard-type correction (DFT+U). However, the parametrization of U is not straightforward due to the lack of reference values, and because ab initio parametrization methods perform poorly. Moreover, SCO complexes undergo notable structural changes upon transition, so intra- and inter-molecular interactions might play an important role in stabilizing either spin state. As a consequence, the U parameter depends strongly on the dispersion correction scheme that is used. In this paper, we parametrize U for nine reported SCO compounds (five based on FeII, 1-5 and four based on FeIII, 6-9) when using the D3 and D3-BJ dispersion corrections. We analyze the impact of the dispersion correction treatments on the SCO energetics, structure, and the unit cell dimensions. The average U values are different for each type of metal ion (FeIIvs. FeIII), and dispersion correction scheme (D3 vs. D3-BJ) but they all show excellent transferability, with mean absolute errors (MAE) below chemical accuracy (i.e. MAE <4 kJ mol-1). This enables a better description of SCO processes and, more generally, of spin state energetics, in materials containing FeII and FeIII ions.
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Metal organic frameworks (MOFs) are increasingly used in applications that rely on the optical and electronic properties of these materials. These applications require a fundamental understanding on how the structure of these materials, and in particular the electronic interactions of the metal node and organic linker, determines these properties. Herein, we report a combined experimental and computational study on two families of lanthanide-based MOFs: Ln-SION-1 and Ln-SION-2. Both comprise the same metal and ligand but with differing structural topologies. In the Ln-SION-2 series the optical absorption is dominated by the ligand and using different lanthanides has no impact on the absorption spectrum. The Ln-SION-1 series shows a completely different behavior in which the ligand and the metal node do interact electronically. By changing the lanthanide in Ln-SION-1, we were able to tune the optical absorption from the UV region to absorption that includes a large part of the visible region. For the early lanthanides we observe intraligand (electronic) transitions in the UV region, while for the late lanthanides a new band appears in the visible. DFT calculations showed that the new band in the visible originates in the spatial orbital overlap between the ligand and metal node. Our quantum calculations indicated that Ln-SION-1 with late lanthanides might be (photo)conductive. Experimentally, we confirm that these materials are weakly conductive and that with an appropriate co-catalysts they can generate hydrogen from a water solution using visible light. Our experimental and theoretical analysis provides fundamental insights for the rational design of Ln-MOFs with the desired optical and electronic properties.
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The reliability of different parameters in the surface hopping method is assessed for a vibronic coupling model of a challenging transition metal complex, where a large number of electronic states of different multiplicities are met within a small energy range. In particular, the effect of two decoherence correction schemes and of various strategies for momentum rescaling and treating frustrating hops during the dynamics is investigated and compared against an accurate quantum dynamics simulation. The results show that surface hopping is generally able to reproduce the reference but also that small differences in the protocol used can strongly affect the results. We find a clear preference for momentum rescaling along only one degree of freedom, using either the nonadiabatic coupling or the gradient difference vector, and trace this effect back to an enhanced number of frustrated hops. Furthermore, reflection of the momentum after frustrated hops is shown to work better than to ignore the process completely. The study also highlights the importance of the decoherence correction, but neither of the two methods employed, energy based decoherence or augmented fewest switches surface hopping, performs completely satisfactory and we trace this effect back to a lack of size-consistency. Finally, the effect of different methods for analyzing the populations is highlighted. More generally, the study emphasizes the importance of the often neglected parameters in surface hopping and shows that there is still a need for simple, robust, and generally applicable correction schemes.
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An accurate modeling of metal-to-ligand-charge-transfer (MLCT) and metal-centered (MC) excited state energies is key to predict the photoinduced response in transition metal complexes (TMCs). Herein, the importance of the ground state and excited state reference geometries is addressed for three-prototype d6 pseudo-octahedral TMCs, each displaying a different potential energy landscape of MLCT versus MC relative stabilities. Several functionals are used within the time-dependent density functional theory (TDDFT), as well as multireference wave-function theory (MS-CASPT2), applied to [Mn(im)(CO)3 (phen)]+ , [Ru(im)2 (bpy)2 ]2+ , and [Re(im)(CO)3 (phen)]+ , (im: imidazole, bpy: bypiridine, phen: phenantroline). The results revel that TDDFT is robust except when using B3LYP functional for first-row d6 TMCs. In contrast, MS-CASPT2 calculations are strongly biased in those cases with competitive MLCT/MC states. The results reinforce the reliability of B3LYP to describe the excited states in d6 TMCs, but question the validity of assessing the density functional theory (DFT)/TDDFT performance via direct comparison with MS-CASPT2 performed at the same DFT reference geometry as a standard strategy. © 2019 Wiley Periodicals, Inc.
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Three new copper(I) complexes [Cu(LX)2]+(PF6-) (where LX stands for 2,9-dihalo-1,10-phenanthroline and X = Cl, Br, and I) have been synthesized in order to study the impact of halogen substituents tethered in the α position of the chelating nitrogen atoms on their physical properties. The photophysical properties of these new complexes (hereafter named Cu-X) were characterized in both their ground and excited states. Femtosecond ultrafast spectroscopy revealed that early photoinduced processes are faster for Cu-I than for Cu-Cl or Cu-Br, both showing similar behaviors. Their electronic absorption and electrochemical properties are comparable to benchmark [Cu(dmp)2]+ (where dmp stands for 2,9-dimethyl-1,10-phenanthroline); furthermore, their optical features were fully reproduced by time-dependent density functional theory and ab initio molecular dynamics calculations. All three complexes are luminescent at room temperature, showing that halogen atoms bound to positions 2 and 9 of phenanthroline are sufficiently bulky to prevent strong interactions between the excited Cu complexes and solvent molecules in the coordination sphere. Their behavior in the excited state, more specifically the extent of the photoluminescence efficiency and its dependence on the temperature, is, however, strongly dependent on the nature of the halogen. A combination of ultrafast transient absorption spectroscopy, temperature-dependent steady-state fluorescence spectroscopy, and computational chemistry allows one to gain a deeper understanding of the behavior of all three complexes in their excited state.
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The electronic excited state reactivity of [Mn(im)(CO)3 (phen)]+ (phen = 1,10-phenanthroline; im = imidazole) ranging between 420 and 330 nm have been analyzed by means of relativistic spin-orbit time-dependent density functional theory and wavefunction approaches (state-average-complete-active-space self-consistent-field/multistate CAS second-order perturbation theory). Minimum energy conical intersection (MECI) structures and connecting pathways were explored using the artificial force induced reaction (AFIR) method. MECIs between the first and second singlet excited states (S1 /S2 -MECIs) were searched by the single-component AFIR (SC-AFIR) algorithm combined with the gradient projection type optimizer. The structural, electronic, and excited states properties of [Mn(im)(CO)3 (phen)]+ are compared to those of the Re(I) analogue [Re(im)(CO)3 (phen)]+ . The high density of excited states and the presence of low-lying metal-centered states that characterize the Mn complex add complexity to the photophysics and open various dissociative channels for both the CO and imidazole ligands. © 2018 Wiley Periodicals, Inc.
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A computational investigation of the triplet excited states of a rhenium complex electronically coupled with a tryptophan side chain and bound to an azurin protein is presented. In particular, by using high-level molecular modeling, evidence is provided for how the electronic properties of the excited-state manifolds strongly depend on coupling with the environment. Indeed, only upon explicitly taking into account the protein environment can two stable triplet states of metal-to-ligand charge transfer or charge-separated nature be recovered. In addition, it is also demonstrated how the rhenium complex plus tryptophan system in an aqueous environment experiences too much flexibility, which prevents the two chromophores from being electronically coupled. This occurrence disables the formation of a charge-separated state. The successful strategy requires a multiscale approach of combining molecular dynamics and quantum chemistry. In this context, the strategy used to parameterize the force fields for the electronic triplet states of the metal complex is also presented.
Assuntos
Azurina/química , Complexos de Coordenação/metabolismo , Pseudomonas aeruginosa/química , Rênio/química , Água/química , Complexos de Coordenação/química , Ligantes , Modelos MolecularesRESUMO
Whereas third row transition metal carbonyl α-diimine complexes display luminescent properties and possess low-lying triplet metal-to-ligand charge transfer (MLCT) states efficiently accessible by a spin-vibronic mechanism, first row analogues hold low-lying metal-centered (MC) excited states that could quench these properties. Upon visible irradiation, different functions are potentially stimulated, namely, luminescence, electron transfer, or photoinduced CO release, the branching ratio of which is governed by the energetics, the character, and the early time dynamics of the photoactive excited states. Simulations of ultrafast nonadiabatic quantum dynamics, including spin-vibronic effects, of [M(imidazole)(CO)3(phenanthroline)]+ (M = Mn, Re) highlight the role of the metal atom. An ultrafast intersystem crossing process, driven by spin-orbit coupling, populates the low-lying triplet states of [Re(imidazole)(CO)3(phen)]+ within the first tens of fs. In contrast, efficient internal conversion between the two lowest 1MLCT states of [Mn(imidazole)(CO)3(phen)]+ is mediated within 50 fs by vibronic coupling with upper MC and MLCT states.
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Optical properties of [Re(CO)3 (dppz)(py)]+ (dppz=dipyrido[3,2-a:2',3'-c]phenazine; py=pyridine) in acetonitrile, water and DNA have been investigated based on DFT, time-dependent-DFT (TD-DFT)/ conductor-like screening model, with and without explicit solvent molecules, and molecular dynamics. Whereas implicit solvent model is not appropriate to model optical properties of dppz-substituted metal complexes, adding explicit solvent molecules in interaction with dppz stabilizes the metal-to-ligand-charge-transfer (MLCT) transitions. Classical molecular dynamics simulations point to an important conformational flexibility, as evidenced by the coexistence of two conformers A and B. When considering the conformational sampling, the lowest band of the absorption spectrum is red-shifted and broadened up to 500â nm in agreement with the experimental spectra supporting important dynamical effects. The absorption spectra of [Re(CO)3 (dppz)(py-R)]+/ GC-DNA and [Re(CO)3 (dppz)(py-R)]+ /AT-DNA (R=CH2 -CH2 -COO- ) intercalated in both major or minor grooves exhibit a lowest energy charge separated (CS) band at about 600â nm and 500â nm, respectively, corresponding mainly to excitations from guanine and adenine to dppz. These states may play a central role into DNA-mediated charge transport processes. The over stabilization of the lowest 3 ILdppz state of [Re(CO)3 (dppz)(py)]+ in water as compared to acetonitrile could be responsible for the quenching of emission in water.