Photoinduced State Research Articles

Light-induced spin-state switching in heterospin complexes of Cu(hfac)2 with pyridine-based nitroxides.

Copper(II)-nitroxide based molecular magnets exhibit spin-crossover-like spin state switching, which is topical in field of molecular magnetism. However, establishing reliable structure-property relationships in these systems is still challenging, especially regarding the light-induced switching of spin states. In this paper, we report the investigation of photoswitching and relaxation in a series of heterospin Cu(hfac)2LR complexes with pyridine-based nitroxide ligands (LR), which belong to this family of materials. Using electron paramagnetic resonance (EPR) for detection, we demonstrate very long lifetimes of photoinduced spin states at liquid helium temperatures (<15 K), where relaxation to the ground state does not exceed 15% within two hours. At the same time, the efficiency of photoswitching strongly depends on the structure of the radical ligand in this series: the bulkier the ligand, the smaller the fraction of heterospin clusters that undergo photoswitching. These findings expand the understanding of mechanisms and factors behind photoswitching and relaxation in copper(II)-nitroxide molecular magnets and aid in further research aiming to optimize their functional properties.

Uncovering excited state behaviours associated with electron-withdrawing CN and electron-donating TPA moieties on SAA derivatives: a theoretical study

Inspired by the excellent photochemical characteristics exhibited by salicylaldehyde azine (SAA) derivatives, our current endeavour primarily revolves around delving into the intricacies of photo-induced excited state reactions for its electron-donating and electron-withdrawing moieties derivatives (i.e. CN-SAA-CN, CN-SAA-TPA and TPA-SAA-TPA). Our simulations reveal push–pull-substituted-dependent photoexcitation that could significantly affect excited state intramolecular proton transfer (ESIPT) reaction for SAA derivatives. Constructing potential energy surfaces (PESs), we unveil the ultrafast ESIPT mechanism due to the low potential barriers. Additionally, by comparing the differences of barriers among CN-SAA-CN, CN-SAA-TPA and TPA-SAA-TPA, we present regulative manner for SAA derivatives by substituting electron-donating and electron-withdrawing moieties. We sincerely anticipate that the modulation of push–pull substitutions on excited state behaviours will pave the way for ground-breaking advancements in luminescent materials.

Uncovering solvent-polarity-associated excited state behaviors for the novel PQ-BSD fluorophore: A theoretical study

In view of the prominent regulated characteristics of electron-donating substituted julolidine-bis(salicylidene)-1,5-diaminonaphthalene (PQ-BSD) derivatives, we are dedicated to exploring photo-induced excited state behaviors of PQ-BSD in solvents. Given the variational solvent polarities, the geometrical changes, infrared (IR) spectral variations, core-valence bifurcation (CVB) indexes as well as charge reorganizations are focused on based on TDDFT method. The strengthened excited-state hydrogen bonding interactions of both hydrogen bonds fully present the excited state intramolecular proton transfer (ESIPT) tendency. Via constructing potential energy surfaces (PESs), the stepwise excited state intramolecular double proton transfer (ESIDPT) process could be revealed for PQ-BSD fluorophore.

Excited-State Dynamics in Segregated Donor-Acceptor Stacks Versus a Peri-Bisdonor-Acceptor System.

The investigation of impact of through-space/through-bond electronic interaction among chromophores on photoexcited-state properties has immense potential owing to the distinct emergent photophysical pathways. Herein, the photoexcited-state dynamics of homo-sorted π-stacked aggregates of a naphthalenemonoimide and perylene-based acceptor-donor (NI-Pe) system and a fork-shaped acceptor-bisdonor (NI-Pe2) system possessing integrally stacked peri-substituted donors was examined. Femtosecond transient absorption (fsTA) spectra of NI-Pe monomer recorded in chloroform displayed spectroscopic signatures of the singlet state of Pe; 1Pe*, the charge-separated state; NI-⋅-Pe+⋅, and the triplet state of Pe; 3Pe*. The examination of ultrafast excited-state processes of NI-Pe aggregate in chloroform revealed faster charge recombination ( =1.75 ns) than the corresponding monomer ( =2.46 ns) which was followed by observation of a broad structureless band attributed to an excimer-like state. The fork-shaped NI-Pe2 displayed characteristic spectroscopic features of the NI radical anion (λmax~450 nm) and perylene dimer radical cation (λmax~520 nm) upon photoexcitation in non-polar toluene solvent in the nanosecond transient absorption (nsTA) spectroscopy. The investigation highlights the significance of intrinsic close-stacked arrangement of donors in ensuring a long-lived photoinduced charge-separated state ( =1.35 μs) in non-polar solvents via delocalization of radical cation between the donors.

Theoretical uncovering of the chalcogen element regulated ESDPT behaviors for 2,5-bis(2-benzoxazolyl)-hydroquinone derivatives.

Inspired by the captivating allure of exquisitely regulated characteristics exhibited by 2-(2-hydroxyphenyl)-benzoxazole and its derivatives in the realms of photochemistry and photophysics, our current endeavor primarily revolves around delving into the intricacies of photo-induced excited state reactions for derivatives of 2,5-bis(2-benzoxazolyl)-hydroquinone (BBHQ). Given the significant impact of chalcogen element doping, herein we predominantly focus on exploring the excited state behaviors of BBHQ-OO, BBHQ-SS, and BBHQ-SeSe fluorophores. Our simulations, resulting from variations in geometry and vertical excitation charge reorganization, reveal atomic-electronegativity-dependent hydrogen bonding interactions and charge recombination induced by photoexcitation that can significantly enhance the excited state intramolecular double proton transfer (ESDPT) reaction for BBHQ-OO, BBHQ-SS, and BBHQ-SeSe fluorophores. By constructing potential energy surfaces (PESs) and identifying transition states (TS), we unveil the ultrafast stepwise ESDPT mechanism due to the low potential barriers. Additionally, by employing heterosubstituted BBHQ-OS and BBHQ-OSe compounds, we rigorously validate the stepwise ESDPT mechanism regulated by chalcogen atomic electronegativity. We sincerely anticipate that the modulation of solvent polarity on excited state behaviors will pave the way for groundbreaking advancements in luminescent materials.

Solvent polarity dependent photo-induced excited state intramolecular proton transfer for triphenylamine centered bis unsymmetrical azine (TPOV): A computational study

The exquisite, regulated characteristics of triphenylamine (TPA) derivatives have served as a profound inspiration in the photochemical field. Herein, the novel TPA-centered bis unsymmetrical azine (i.e., 3-methoxysalicylaldehyde substituted 4-((E)-hydrazonomethyl)-N-(4-((E)-hydrazonomethyl)phenyl)-N-phenylaniline (TPOV)) is investigated regarding its photo-induced behaviors and excited state intramolecular proton transfer (ESIPT) mechanisms. Solvent polar-dependent hydrogen bonding interactions and charge recombination, which is induced by photoexcitation, can greatly promote the ESIPT reactions of the TPOV chemosensor. In order to unveil the detailed excited state reaction mechanism, we theoretically construct the S0-state and S1-state of potential energy surfaces (PESs). Based on the S1-state PESs for TPOV in toluene, chloroform, and acetonitrile solvents, we unveil the single ESIPT reaction of TPOV that happens along with alternative dual intramolecular hydrogen bonds (O1-H2···N3 and O4-H5···N6). The solvent polarity-regulated excited state might clear the path for the creation of innovative luminescent materials.

Computational explorations about the solvent-polarity-associated excited state proton transfer behaviors for the novel F-BSD compound.

Inspired by the excellent potential application prospects from the precisely controlled attributes displayed by fluorine-substituted-bis(salicylidene)-1,5-diaminonaphthalene (F-BSD) and its derivatives in the domains of photochemistry and photophysics, our present undertaking predominantly focuses on exploring the complexities of photo-induced excited state reactions for F-BSD fluorophores dissolved in solvents with diverse levels of polarity. Our simulations reveal that the excited state intramolecular double proton transfer (ESIDPT) reaction for F-BSD chemosensor can be significantly regulated by solvent polarity-dependent hydrogen bonding interactions and charge recombination induced by photoexcitation, which result from variations in geometries and vertical excitation charge reorganizations. By constructing potential energy surfaces (PESs), we also demonstrate that the stepwise ESIDPT reaction of F-BSD occurs with alternative dual intramolecular hydrogen bonds (O1-H2···N3 or O4-H5···N6). Interestingly, we affirm polar solvents should be conducive to the first-step of ESIDPT process, while nonpolar solvents are in favor of the second step. We sincerely hope solvent polarity-dependent ESIDPT behavior will pave the way for future design of novel luminescent materials. The molecular geometries were optimized by DFT//TDDFT D3-B3LYP/TZVP theoretical level with IEFPCM solvent model in S0 and S1 states, respectively. This work also explores the energy level of target molecules with the computational vertical absorption spectra by TDDFT. All the simulations were carried out based on Gaussian 16 software. The core-valence bifurcation (CVB) indexes were obtained by using Multiwfn 3.8. Potential energy surfaces were constructed by the DFT//TDDFT D3-B3LYP/TZVP level based on restricted optimization, also the transition state (TS) forms were searched using the same level.

Aggregation-Driven Photoinduced α-C(sp3)-H Bond Hydroxylation/C(sp3)-C(sp3) Coupling of Boron Dipyrromethene Dye in Water Reported by Near-Infrared Emission.

Molecular aggregation is a powerful tool for tuning advanced materials' photophysical and electronic properties. Here we present a novel potential for the aqueous-solvated aggregated state of boron dipyrromethene (BODIPY) to facilitate phototransformations otherwise achievable only under harsh chemical conditions. We show that the photoinduced symmetry-breaking charge separation state can itself initiate catalyst-free redox chemistry, leading to selective α-C(sp3)-H bond activation/Csp3-Csp3 coupling on the BODIPY backbone. The photoproduction progress was tracked by monitoring the evolution of the strong Stokes-shifted near-infrared emission, resulting from selective self-assembly of the terminal heterodimeric photoproduct into well-ordered J-aggregates, as revealed by X-ray structural analysis. These findings provide a facile and green route to further explore the promising frontier of packing-triggered selective photoconversions via supramolecular engineering.

Ultrafast Raman thermometry in driven YBa2Cu3O6.48

Signatures of photoinduced superconductivity have been reported in cuprate materials subjected to a coherent phonon drive. A “cold” superfluid was extracted from the transient Terahertz conductivity and was seen to coexist with “hot” uncondensed quasiparticles, a hallmark of a driven-dissipative system of which the interplay between coherent and incoherent responses is not well understood. Here, time resolved spontaneous Raman scattering was used to probe the lattice temperature in the photoinduced superconducting state of YBa2Cu3O6.48. An increase in lattice temperature of up to 140 K was observed by measuring the time dependent Raman scattering intensity of an undriven “spectator” phonon mode. This value is consistent with the estimated increase in quasiparticle temperature measured under the same excitation conditions. These temperature changes provide quantitative information on the nature of the driven state and its decay, and may suggest a strategy to optimize this effect. Published by the American Physical Society 2024

Correlating Valence and 2p3d RIXS Spectroscopies: A Ligand-Field Study of Spin-Crossover Iron(II).

The molecular spin-crossover phenomenon between high-spin (HS) and low-spin (LS) states is a promising route to next-generation information storage, sensing applications, and molecular spintronics. Spin-crossover complexes also provide a unique opportunity to study the ligand field (LF) properties of a system in both HS and LS states while maintaining the same ligand environment. Presently, we employ complementing valence and core-level spectroscopic methods to probe the electronic excited-state manifolds of the spin-crossover complex [FeII(H2B(pz)2)2phen]0. Light-induced excited spin-state trapping (LIESST) at liquid He temperatures is exploited to characterize magnetic and spectroscopic properties of the photoinduced HS state using SQUID magnetometry and magnetic circular dichroism spectroscopy. In parallel, Fe 2p3d RIXS spectroscopy is employed to examine the ΔS = 0, 1 excited LF states. These experimental studies are combined with state-of-the-art CASSCF/NEVPT2 and CASCI/NEVPT2 calculations characterizing the ground and LF excited states. Analysis of the acquired LF information further supports the notion that the spin-crossover of [FeII(H2B(pz)2)2phen]0 is asymmetric, evidenced by a decrease in eπ in the LS state. The results demonstrate the power of cross-correlating spectroscopic techniques with high and low LF information content to make accurate excited-state assignments, as well as the current capabilities of ab initio theory in interpreting these electronic properties.

Insight into solvent-polarity-regulated photoinduced excited state behaviors for E-HBT fluorophore: a theoretical investigation

Insight into solvent-polarity-regulated photoinduced excited state behaviors for E-HBT fluorophore: a theoretical investigation

Substitution effects on the photoinduced excited state dynamics of perylenemonoimides in solution and thin films.

Perylene monoimide (PMI) derivatives are attracting significant attention due to their strong absorption in the visible range, thermal stability, and synthetic accessibility. These properties make them promising for application in various areas such as optoelectronic devices, photosensitizers, etc. In this work, the photophysical properties and excited state dynamics of four different PMI derivatives (PMIB, BrPMITB, PMITB, and APITB) were studied in solution and thin films utilizing steady-state and time-resolved spectroscopic techniques. Among the four PMI derivatives, APITB is designed as a donor-acceptor dyad, with thianthrene as a donor and PMI as an acceptor. The activation of the triplet state through the spin-orbit charge transfer intersystem crossing (SOCT-ISC) process in THF was observed upon substitution with the thianthrene group at the peri position of the PMI moiety. The SOCT-ISC process facilitates triplet formation in the APITB dyad within 423 ps. Meanwhile, other PMI derivatives showed fluorescence within the femtosecond timescale in THF. The PMI derivatives in thin films displayed different photo physical properties to those in THF. This discrepancy arises due to the effective intermolecular coupling between the PMI derivatives in thin films.

Photochromism and single-component white light emission from a metalloviologen complex based on 1,5-naphthyridine.

Metalloviologens, as emerging electron-transfer photochromic compounds, have shown intriguing properties such as radiochromism, photochromism and photoconductance. However, only a limited number of them have been reported so far. Exploration of new metalloviologens is strongly desired. Herein, we report a new solvothermally synthesized metalloviologen complex [CdCl2(ND)2]n (1, ND = 1,5-naphthalenes) that exhibits photochromic and intrinsic white light emission properties. Density functional theory calculation results reveal that the photochromism could be assigned to photoinduced electron transfer from chlorine atoms to ND molecules. The photoinduced charge-separated states are heat/air stable, attributed to the delocalization of ND and strong intermolecular π-π interactions. Besides, complex 1 consistently emits intrinsic white light when excited with 340-370 nm UV light, achieving high color rendering index (CRI) values (82.54-94.04). By adjusting the excitation wavelength, both "warm" and "cold" white light emission can be produced, making it suitable for the application of a white light emitting diode (WLED). Thus, this work demonstrates that the ND-based metalloviologen is not only helpful in producing photochromism, but also beneficial for creating white-light emission.

Out-of-equilibrium dynamics of a grid-like Fe(ii) spin crossover dimer triggered by a two-photon excitation.

The application of two-photon excitation (TPE) in the study of light-responsive materials holds immense potential due to its deeper penetration and reduced photodamage. Despite these benefits, TPE has been underutilised in the investigation of the photoinduced spin crossover (SCO) phenomenon. Here, we employ TPE to delve into the out-of-equilibrium dynamics of a SCO FeII dimer of the form [FeII(HL)2]2(BF4)4·2MeCN (HL = 3,5-bis{6-(2,2'-bipyridyl)}pyrazole). Optical transient absorption (OTA) spectroscopy in solution proves that the same dynamics take place under both one-photon excitation (OPE) and TPE. The results show the emergence of the photoinduced high spin state in less than 2 ps and with a lifetime of 147 ns. Time-resolved photocrystallography (TRXRD) reveals a single molecular reorganisation within the first 500 ps following TPE. Additionally, variable temperature single crystal X-ray diffraction (VTSCXRD) and magnetic susceptibility measurements confirm that the thermal transition is silenced by the solvent. While the results of the OTA and TRXRD utilising TPE are intriguing, the high pump fluencies required to excite enough metal centres to the high spin state may impair its practical application. Nonetheless, this study sheds light on the potential of TPE for the investigation of the out-of-equilibrium dynamics of SCO complexes.

Reversible CO2 Capture and On-Demand Release by an Acidity-Matched Organic Photoswitch.

Separation of carbon dioxide (CO2) from point sources or directly from the atmosphere can contribute crucially to climate change mitigation plans in the coming decades. A fundamental practical limitation for the current strategies is the considerable energy cost required to regenerate the sorbent and release the captured CO2 for storage or utilization. A directly photochemically driven system that demonstrates efficient passive capture and on-demand CO2 release triggered by sunlight as the sole external stimulus would provide an attractive alternative. However, little is known about the thermodynamic requirements for such a process or mechanisms for modulating the stability of CO2-derived dissolved species by using photoinduced metastable states. Here, we show that an organic photoswitchable molecule of precisely tuned effective acidity can repeatedly capture and release a near-stoichiometric quantity of CO2 according to dark-light cycles. The CO2-derived species rests as a solvent-separated ion pair, and key aspects of its excited-state dynamics that regulate the photorelease efficiency are characterized by transient absorption spectroscopy. The thermodynamic and kinetic concepts established herein will serve as guiding principles for the development of viable solar-powered negative emission technologies.

Theoretical insights into the photophysics of an unnatural base Z: A MS-CASPT2 investigation.

We have employed the highly accurate multistate complete active space second-order perturbation theory (MS-CASPT2) method to investigate the photoinduced excited state relaxation properties of one unnatural base, namely Z. Upon excitation to the S2 state of Z, the internal conversion to the S1 state would be dominant. From the S1 state, two intersystem crossing paths leading to the T2 and T1 states and one internal conversion path to the S0 state are possible. However, considering the large barrier to access the S1 /S0 conical intersection and the strong spin-orbit coupling between S1 and T2 states (>40 cm-1 ), the intersystem crossing to the triplet manifolds is predicted to be more preferred. Arriving at the T2 state, the internal conversion to the T1 state and the intersystem crossing back to the S1 state are both possible considering the S1 /T2 /T1 three-state intersection near the T2 minimum. Upon arrival at the T1 state, the deactivation to S0 can be efficient after overcoming a small barrier to access T1 /S0 crossing point, where the spin-orbit coupling (SOC) is as large as 39.7 cm-1 . Our present work not only provides in-depth insights into the photoinduced process of unnatural base Z, but can also help the future design of novel unnatural bases with better photostability.

Dominant Role of Hole Transport Pathway in Achieving Record High Photoconductivity in Two-Dimensional Metal-Organic Frameworks.

Metal-organic frameworks (MOFs) with mobile charges have attracted significant attention due to their potential applications in photoelectric devices, chemical resistance sensors, and catalysis. However, fundamental understanding of the charge transport pathway within the framework and the key properties that determine the performance of conductive MOFs in photoelectric devices remain underexplored. Herein, we report the mechanisms of photoinduced charge transport and electron dynamics in the conductive 2D M-HHTP (M=Cu, Zn or Cu/Zn mixed; HHTP=2,3,6,7,10,11-hexahydroxytriphenylene) MOFs and their correlation with photoconductivity using the combination of time-resolved terahertz spectroscopy, optical transient absorption spectroscopy, X-ray transient absorption spectroscopy, and density functional theory (DFT) calculations. We identify the through-space hole transport mechanism through the interlayer sheet π-π interaction, where photoinduced hole state resides in HHTP ligand and electronic state is localized at the metal center. Moreover, the photoconductivity of the Cu-HHTP MOF is found to be 65.5 S m-1 , which represents the record high photoconductivity for porous MOF materials based on catecholate ligands.

Dominant Role of Hole Transport Pathway in Achieving Record High Photoconductivity in Two‐Dimensional Metal–Organic Frameworks

AbstractMetal–organic frameworks (MOFs) with mobile charges have attracted significant attention due to their potential applications in photoelectric devices, chemical resistance sensors, and catalysis. However, fundamental understanding of the charge transport pathway within the framework and the key properties that determine the performance of conductive MOFs in photoelectric devices remain underexplored. Herein, we report the mechanisms of photoinduced charge transport and electron dynamics in the conductive 2D M−HHTP (M=Cu, Zn or Cu/Zn mixed; HHTP=2,3,6,7,10,11‐hexahydroxytriphenylene) MOFs and their correlation with photoconductivity using the combination of time‐resolved terahertz spectroscopy, optical transient absorption spectroscopy, X‐ray transient absorption spectroscopy, and density functional theory (DFT) calculations. We identify the through‐space hole transport mechanism through the interlayer sheet π–π interaction, where photoinduced hole state resides in HHTP ligand and electronic state is localized at the metal center. Moreover, the photoconductivity of the Cu−HHTP MOF is found to be 65.5 S m−1, which represents the record high photoconductivity for porous MOF materials based on catecholate ligands.

Photo-physical characterization of high triplet yield brominated fluoresceins by transient state (TRAST) spectroscopy

Photo-induced dark transient states of fluorophores can pose a problem in fluorescence spectroscopy. However, their typically long lifetimes also make them highly environment sensitive, suggesting fluorophores with prominent dark-state formation yields to be used as microenvironmental sensors in bio-molecular spectroscopy and imaging. In this work, we analyzed the singlet–triplet transitions of fluorescein and three synthesized carboxy-fluorescein derivatives, with one, two or four bromines linked to the anthracence backbone. Using transient state (TRAST) spectroscopy, we found a prominent internal heavy atom (IHA) enhancement of the intersystem crossing (ISC) rates upon bromination, inferred by density functional theory calculations to take place via a higher triplet state, followed by relaxation to the lowest triplet state. A corresponding external heavy atom (EHA) enhancement was found upon adding potassium iodide (KI). Notably, increased KI concentrations still resulted in lowered triplet state buildup in the brominated fluorophores, due to relatively lower enhancements in ISC, than in the triplet decay. Together with an antioxidative effect on the fluorophores, adding KI thus generated a fluorescence enhancement of the brominated fluorophores. By TRAST measurements, analyzing the average fluorescence intensity of fluorescent molecules subject to a systematically varied excitation modulation, dark state transitions within very high triplet yield (>90%) fluorophores can be directly analyzed under biologically relevant conditions. These measurements, not possible by other techniques such as fluorescence correlation spectroscopy, opens for bio-sensing applications based on high triplet yield fluorophores, and for characterization of high triplet yield photodynamic therapy agents, and how they are influenced by IHA and EHA effects.

Tuning ultrafast time-evolution of photo-induced charge-transfer states: A real-time electronic dynamics study in substituted indenotetracene derivatives.

Photo-induced charge transfer (CT) states are pivotal in many technological and biological processes. A deeper knowledge of such states is mandatory for modeling the charge migration dynamics. Real-time time-dependent density functional theory (RT-TD-DFT) electronic dynamics simulations are employed to explicitly observe the electronic density time-evolution upon photo-excitation. Asymmetrically substituted indenotetracene molecules, given their potential application as n-type semiconductors in organic photovoltaic materials, are here investigated. Effects of substituents with different electron-donating characters are analyzed in terms of the overall electronic energy spacing and resulting ultrafast CT dynamics through linear response (LR-)TD-DFT and RT-TD-DFT based approaches. The combination of the computational techniques here employed provided direct access to the electronic density reorganization in time and to its spatial and rational representation in terms of molecular orbital occupation time evolution. Such results can be exploited to design peculiar directional charge dynamics, crucial when photoactive materials are used for light-harvesting applications.