Relaxed S1 Research Articles

Mono- and Bichromophores Formed from Perylene Monoimide Diesters: Competition between Intramolecular Charge Transfer and Intermolecular Singlet Exciton Fission.

Perylene monoimide diesters and the corresponding phenyl-linked bichromophores are strongly fluorescent in dilute solution with minimal triplet population after relaxation of the initial Franck-Condon state. The monomer forms nonemissive face-to-face dimers in solution, wherein illumination leads to formation of a spin-correlated, triplet pair with a yield of ca. 13% and with a time constant of 4 ± 1 ps. The triplet pair, which is localized on the aggregate, cannot separate and decays with a mean lifetime of 80 ± 10 ps. The relaxed S1 state of the weakly coupled, phenyl-linked bichromophores establishes an equilibrium with an intramolecular charge-transfer state over a hundred picoseconds or so, depending on the solvent and the geometry of the linkage. This equilibrium mixture, being dominated by the relaxed S1 state, decays on the nanosecond time scale in solution at room temperature without implication of a triplet state. Self-association occurs at higher concentration and, for the para-bridged bichromophore, leads to inefficient triplet formation in tetrahydrofuran at room temperature.

Anisole-Water and Anisole-Ammonia Complexes in Ground and Excited (S1) States: A Multiconfigurational Symmetry-Adapted Perturbation Theory (SAPT) Study.

Binary complexes of anisole have long been considered paradigm systems for studying microsolvation in both the ground and electronically excited states. We report a symmetry-adapted perturbation theory (SAPT) analysis of intermolecular interactions in anisole-water and anisole-ammonia complexes within the framework of the multireference SAPT(CAS) method. Upon the S1 ← S0 electronic transition, the hydrogen bond in the anisole-water dimer is weakened, which SAPT(CAS) shows to be determined by changes in the electrostatic energy. As a result, the water complex becomes less stable in the relaxed S1 state despite decreased Pauli repulsion. Stronger binding of the anisole-ammonia complex following electronic excitation is more nuanced and results from counteracting shifts in the repulsive (exchange) and attractive (electrostatic, induction and dispersion) forces. In particular, we show that the formation of additional binding N-H···π contacts in the relaxed S1 geometry is possible due to reduced Pauli repulsion in the excited state. The SAPT(CAS) interaction energies have been validated against the coupled cluster (CC) results and experimentally determined shifts of the S1 ← S0 anisole band. While for the hydrogen-bonded anisole-water dimer SAPT(CAS) and CC shifts are in excellent agreement, for ammonia SAPT(CAS) is only qualitatively correct.

Femtosecond to Microsecond Observation of Photochemical Pathways in Nitroaromatic Phototriggers Using Transient Absorption Spectroscopy.

The synthetic accessibility and tolerance to structural modification of phototriggered compounds (PTs) based on the ortho- nitrobenzene (ONB) protecting group have encouraged a myriad of applications including optimization of biological activity, and supramolecular polymerization. Here, a combination of ultrafast transient absorption spectroscopy techniques is used to study the multistep photochemistry of two nitroaromatic phototriggers based on the ONB chromophore, O-(4,5-dimethoxy-2-nitrobenzyl)-l-serine (DMNB-Ser) and O-[(2-nitrophenyl)methyl]-l-tyrosine hydrochloride (NB-Tyr), in DMSO solutions on femtosecond to microsecond time scales following the absorption of UV light. From a common nitro-S1 excited state, the PTs can either undergo excited state intramolecular hydrogen transfer (ESIHT) to an aci-S1 isomer within the singlet state manifold, leading to direct S1 → S0 internal conversion through a conical intersection, or competitive intersystem crossing (ISC) to access the triplet state manifold on time scales of (1.93 ± 0.03) ps and (13.9 ± 1.2) ps for DMNB-Ser and NB-Tyr, respectively. Deprotonation of aci-T1 species to yield triplet anions is proposed to occur in both PTs, with an illustrative time constant of (9.4 ± 0.7) ns for DMNB-Ser. More than 75% of the photoexcited molecules return to their electronic ground states within 8 μs, either by direct S1 → S0 relaxation or anion reprotonation. Hence, upper limits to the quantum yields of photoproduct formation are estimated to be in the range of 13-25%. Mixed DMSO/H2O solvents show the influence of the environment on the observed photochemistry, for example, revealing two nitro-S1 lifetimes for DMNB-Ser in a 10:1 DMSO/H2O mixture of 1.95 ps and (10.1 ± 1.2) ps, which are attributed to different microsolvation environments.

Raman Vibrational Signatures of Excited States of Echinenone in the Orange Carotenoid Protein (OCP) and Implications for its Photoactivation Mechanism

In this study, the vibrational characteristics of optically excited echinenone in various solvents and the Orange Carotenoid Protein (OCP) in red and orange states are systematically investigated through steady-state and time-resolved spectroscopy techniques. Time-resolved experiments, employing both Transient Absorption (TA) and Femtosecond Stimulated Raman Spectroscopy (FSRS), reveal different states in the OCP photoactivation process. The time-resolved studies indicate vibrational signatures of exited states positioned above the S1 state during the initial 140 fs of carotenoid evolution in OCP, an absence of a vibrational signature for the relaxed S1 state of echinenone in OCP, and more robust signatures of a highly excited ground state (GS) in OCP. Differences in S1 state vibration population signatures between OCP and solvents are attributed to distinct conformations of echinenone in OCP and hydrogen bonds at the keto group forming a short-lived intramolecular charge transfer (ICT) state. The vibrational dynamics of the hot GS in OCP show a more pronounced red shift of ground state CC vibration compared to echinenone in solvents, thus suggesting an unusually hot form of GS. The study proposes a hypothesis for the photoactivation mechanism of OCP, emphasizing the high level of vibrational excitation in longitudinal stretching modes as a driving force. In conclusion, the comparison of vibrational signatures reveals unique dynamics of energy dissipation in OCP, providing insights into the photoactivation mechanism and highlighting the impact of the protein environment on carotenoid behavior. The study underscores the importance of vibrational analysis in understanding the intricate processes involved in early phase OCP photoactivation.

Modulation of lanthanide luminescence by carbamoylmethylphosphine oxide ligand: A theoretical study

The antenna capacity of Phenacyldiphenylphosphine oxide (Phenac), combining C=O and P=O donor groups was established by theoretical examination of its chromophore properties, binding ability to encapsulate and stabilize lanthanide complexes and potential to sensitize the EuIII and TbIII luminescence in Eu(Phenac)2(NO3)3(H2O) (1), Eu(Phenac)2(NO3)3 (2), Eu(Phenac)3(NO3)3 (3) and Tb(Phenac)2(NO3)3(H2O) (4) complexes in vacuum, solution and solid phase. The ligand-centered singlet and triplet excited state energies, the rates and lifetimes for the rival nonradiative (S1→T1,2 intersystem crossing (ISC)) and radiative and nonradiative S1→S0 and T1→S0 relaxation were predicted by means of DFT/TDDFT/ωB97XD calculations. Similar relaxation paths were found for all complexes. The absorbed energy by Sn > 1(π-π*) states relaxed to T1min by major ISC mechanism S1→T2→T1. The long radiative lifetime of S1→S0 due to n(p(C)(O))π-π*,p(P) character facilitated the forward ISC process. The environment, Phenac's number and LnIII size affect the T1 energy ∼0.1 eV. The calculated (Phenac→EuIII) energy transfer rates suggested the most likely T1 → 5D1/5D0 channels for a population of emitting metal-centered states. The small Φ of EuIII and larger luminescence of TbIII were discussed and explained. The importance of the P=O and C=O groups for the coordination ability and absorption properties of Phenac has been elucidated.

Solvation controlled excited-state dynamics in a donor-acceptor phenazine-imidazole derivative.

In the past few decades, significant efforts have been devoted to developing phenazine derivatives in various fields such as medicine, pesticides, dyes, and conductive materials owing to their highly Stokes-shifted fluorescence and distinctive photophysical properties. The modulation of the surrounding environment can effectively influence the luminescent behavior of phenazine derivatives, prompting us to investigate the solvent effect on the excited state dynamics. Herein, we present the solvent controlled excited state dynamics of a novel triphenylamine-based phenazine-imidazole molecule (TPAIP) through steady-state spectra and femtosecond transient absorption spectra. The fluorescence emission spectrum exhibited a redshift with increasing solvent polarity, indicating the existence of a charge transfer state. Furthermore, by tracking the femtosecond transient absorption spectra of TPAIP, we found that the nature of the relaxed S1 state was strongly influenced by the solvent polarity: intersystem crossing character appears in apolar solvent, whereas intramolecular charge transfer character occurs in polar solvent because of solvation. These findings provide significant theoretical insights into the impact of solvents on the excited state dynamics within phenazine derivatives. This understanding supports diverse applications ranging from advanced biological probe design to photocatalysis and pharmaceutical research.

Dynamic Role of the Intramolecular Hydrogen Bonding in the S1 State Relaxation Dynamics Revealed by the Direct Measurement of the Mode-Dependent Internal Conversion Rate of 2-Chlorophenol and 2-Chlorothiophenol.

The dynamic role of the intramolecular hydrogen bond in the S1 relaxation of cis-2-chlorophenol (2-CP) or cis-2-chlorothiophenol (2-CTP) has been investigated in a state-specific manner. Whereas ultrafast internal conversion is dominant for 2-CP, the H-tunneling competes with internal conversion for 2-CTP even at the S1 origin. The S0-S1 internal conversion rate of 2-CTP could be directly measured from the S1 lifetimes of 2-CTP-d1 (Cl-C6H4-SD) as the D-tunneling is kinetically blocked, allowing distinct estimations of tunneling and internal conversion rates with increasing the energy. The internal conversion rate of 2-CTP increases by two times at the out-of-plane torsional mode excitation, suggesting that the internal conversion is facilitated at the nonplanar geometry. It then sharply increases at ∼600 cm-1, indicating that the S1/S0 conical intersection is readily accessible at the extended C-Cl bond length. The strength of the intramolecular hydrogen bond should be responsible for the distinct dynamic behaviors of 2-CP and 2-CTP.

Symmetrically Functionalized Copper and Silver Corrole-Bis-Tetracyanobutadiene Push-Pull Conjugates: Efficient Population of Triplet States via Charge Transfer.

Copper and silver tritolylcorroles (TTC) are symmetrically functionalized to carry two tetracyanobutadiene (TCBD) entities via [2+2] cycloaddition-retroeletrocyclization reaction involving ethynyl functionalized corroles with an electron acceptor, tetracyanoethylene (TCNE) in excellent yields, as the first examples of corrole-TCBD push-pull systems. The strong push-pull effect resulted in charge polarization in the ground state resulting in a considerable hypsochromic shift of the spectrum extending it into the near-IR region. Electrochemical studies coupled with computational studies revealed considerable interactions between the two TCBD entities via the corrole π-system and the degree of such interactions was found to depend on the metal ion present in the corrole cavity. Energy considerations suggested charge transfer (CT) from the S2 or vibrationally hot S1 state but not the relaxed S1 state in the case of CuTTC(TCBD)2 while CT to occur from all these states in the case of AgTTC(TCBD)2 . Additionally, the high-energy CT states populate the low-lying triplet states. Systematic femtosecond pump-probe studies provided the ultimate proof for the occurrence of excited CT as a function of excitation wavelength followed by the efficient population of the triplet states. The present study brings out the significance of charge transfer in efficiently populating the triplet states in rather unusual copper and silver corroles carrying two TCBD entities.

Organic solar cells and their applications Shah, Razon Oda, F. Hazuan

Enhancing the power conversion efficiency (PCE) is the ma- jor task in the development of solar cells. In 1961, Willi- am Shockley and Hans J. Queisser pointed out that the highest PCE for a single-junction solar cell is limited to 31% due to the thermalization and transmission losses. Singlet fission (SF) is an appealing carrier-multiplication approach to break the Shockley-Queisser limit, since it converts one high- energy singlet exciton into two low-energy triplet excitons. Thus, one absorbed photon generates two electron–hole pairs [1]. SF phenomenon was first observed in anthracene single crystals in 1965. It attracted attention again in 2006. In organic semiconductors, a singlet exciton (S1) forms after the ab- sorption of a photon. If the energy of this singlet exciton is greater than twice of that for triplet exciton (T1), namely E(S1) > 2E(T1), then spin-allowed fission (S1 → 2T 1) could occur. The general kinetic model for SF process is S0 is the ground state, S1 is the excited singlet state, 1(TT) is the intermediate state of a correlated triplet pair, and T1 + T1 are two independent triplet states (Figure 1(a)). The application needs materials with high fission efficiency, suitable bandgap for capturing high-energy photons, appropriate triplet energy and high chemical stability. Owing to the existence of competitive pathways (i.e. S1 to S0 relaxation in picosecond–nanosecond timescale; excimer formation in femtosecond timescale; charge transfer (CT) process in femtosecond timescale, SF needs to occur in pico- second or sub-picosecond timescale. Thus, SF requires strong intermolecular coupling. The intermolecular coupling can be realized via Van der Waals force, weak non-bonded interactions and so on. The coupling distance not only affects SF rate and triplet yield, but also influences the lifetime and diffusion length of triplet excitons [2].

Dynamics and mechanisms of nonradiative photodissociation of glycine: A theoretical study

Photochemistry of small biomolecules is fundamental to understand the photochemical reactions of larger molecules, such as proteins. In this work, the dynamics and mechanisms of photodissociations of glycine conformers were studied using the DFT, TD-DFT and CASPT2 methods with the aug-cc-pVDZ basis set and microcanonical molecular dynamics simulations with surface hopping dynamics (NVE-MDSH). This study emphasized unimolecular dissociations and isomerization, nonradiative S1 → S0 relaxations that generate molecular products and the interplay between photoenergies and thermal energies. Four nonplanar conformers were suggested by the TD-DFT/B3LYP/aug-cc-pVDZ and CASPT2(8,14)/aug-cc-pVDZ methods to be stable in the S1 state. The potential energy curves obtained from the TD-DFT/B3LYP/aug-cc-pVDZ and CASPT2(8,14)/aug-cc-pVDZ methods and SA-CPMCSCF/6-31G(d) conical intersection optimizations suggested S0/S1 intersections for distorted glycine structures, Cα–N and NH dissociations and NH → OC isomerization. The NVE-MDSH results showed that although no dissociated molecular product was observed in the S1 state, isomerization-mediated dissociation and exothermic S1 → S0 relaxation temperature could lead to eight molecular product channels, in which the vertically excited Wigner-sampled structures generated eleven reactive and stable molecular products in different temperature ranges. These thermally selective reactions favored the lowest energy conformer (structure Ip) as the precursor, from which reactive and stable molecular products were formed above the threshold exothermic relaxation temperature. These theoretical results showed in detail for the first time how unimolecular photodissociations and nonradiative S1 → S0 relaxations create molecules in cold interstellar media without heat transfer from the surroundings. The results in this work could be used in future theoretical and experimental studies on the same or similar systems.

Photoluminescence and scintillation of Sn2+-doped gadolinium aluminum-silicate glasses

The photoluminescence and scintillation properties of Sn2+-doped gadolinium aluminum-silicate Gd2O3–Al2O3–SiO2 (GAS) glasses with Si3N4 as reducing agent were investigated. The glasses showed a wide emission band in the range of 360–730 nm due to the relaxation of S1–S0 and T1-S0 of Sn2+ luminescent centers. The luminescent intensity of Sn2+-doped GAS glasses reaches maximum at 0.3 mol% Sn2+. The lifetimes of the glasses vary between 6 and 12 μs, which related to the full width at half maximum (FWHM) of the emission spectra. Different oxides were added to explore the relationship between optical basicity and the luminescent properties of glasses. The addition of B2O3 increases the photoluminescence quantum yield (PL QY) of the glasses, which is due to reduction of the Stokes shift and increment of radiative transition probability in energy level transition. The X-ray induced scintillation luminescence of the glasses were observed and studied.

Synthesis and Properties of 1‐(Dialkylstannyl)‐1,4‐diphenyl‐1,3‐butadiene Fused with a Dibenzobarrelene and the Corresponding Pentaorganostannate

Abstract1‐(Dialkylstannyl)‐1,4‐diphenyl‐1,3‐butadiene derivatives that fuse with a dibenzobarrelene were synthesized by the reaction of the dilithium salt, prepared by the treatment of the corresponding tellurium analogue with BuLi, with R2SnCl2 (R=Me or Bu). When Me2SnCl2 was used, a Me−Bu exchange (Bu is from BuLi) was observed. The dimethyl‐, butylmethyl‐, and dibutylstannyl derivatives exhibit weak fluorescence in solution and the solid state. The dibutylstannyl derivative reacted with BuLi in THF to give a pentaorganostannate, which was characterized by means of 119Sn NMR and UV‐vis spectroscopies. Their optical properties were analyzed with TD‐DFT calculations. The first excitation of dialkylstannyl derivatives is assigned to the π‐π* excitation, and an intersystem crossing from the relaxed S1 state to a triplet state was suggested. The calculations show that the dark red color of the pentaorganostannate is ascribed to the excitation from the hypervalent Sn−C bonds (σ) to the π* orbital of the 1,4‐diphenyl‐1,3‐butadiene moiety.

Direct Tracking Excited-State Intramolecular Charge Redistribution of Acceptor-Donor-Acceptor Molecule by Means of Femtosecond Stimulated Raman Spectroscopy.

Symmetric quadrupolar molecules generally exhibit apolar ground states and dipolar excited states in a polar environment, which is explained by the excited state evolution from initial charge delocalization over all molecules to localization on one branch of the molecules after a femtosecond pulse excitation. However, direct observation of excited-state charge redistribution (delocalization/localization) is hardly accessible. Here, the intramolecular charge delocalization/localization character of a newly synthesized acceptor-donor-acceptor molecule (ADA) has been intensively investigated by femtosecond stimulated Raman scattering (FSRS) together with femtosecond transient absorption (fs-TA) spectroscopy. By tracking the excited state Raman spectra of the specific alkynyl (-C≡C-) bonds at each branch of ADA, we found that the nature of the relaxed S1 state is strongly governed by solvent polarity: symmetric delocalized intramolecular charge transfer (ICT) characters occurred in apolar solvent, whereas the asymmetric localized ICT characters appeared in polar solvent because of solvation. The solvation dynamics of ADA extracted from fs-TA is consistent with the time constants obtained by FSRS, but the FSRS clearly tracks the excited state intramolecular charge transfer delocalization/localization.

Excited-State Evolution of Keto-Carotenoids after Excess Energy Excitation in the UV Region.

Carotenoids are molecules with rich photophysics that are in many biological systems involved in photoprotection. Yet, their response to excess energy excitation is only scarcely studied. Here we have explored excited state properties of three keto-carotenoids, echinenone, canthaxanthin and rhodoxanthin after excess energy excitation to a singlet state absorbing in UV. Though the basic spectral features and kinetics of S2 , hot S1 , relaxed S1 states remain unchanged upon UV excitation, the clear increase of the S* signal is observed after excess energy excitation, associated with increased S* lifetime. A multiple origin of the S* signal, originating either from specific conformations in the S1 state or from a non-equilibrated ground state, is confirmed in this work. We propose that the increased amount of energy stored in molecular vibrations, induced by the UV excitation, is the reason for the enhanced S* signal observed after UV excitation. Our data also suggest that a fraction of the UV excited state population may proceed through a non-sequential pathway, bypassing the S2 state.

Investigation of Morphology-Controlled Ultrafast Relaxation Processes of Aggregated Porphyrin.

Here, we have synthesized rod and flake shaped morphology of porphyrin aggregates from 5, 10, 15, 20-tetra (4-n-octyloxyphenyl) porphyrin (4-opTPP) molecule which are evident from scanning electron microscopy (SEM). The formation of J-type aggregation is evident from steady state and time-resolved fluorescence spectroscopic studies. Ultrafast transient absorption spectroscopic studies reveal that the excited state lifetime is controlled by the morphology and the time constant for S1→S0 relaxation changes from 3.05 ps to 744 ps with changing the shape from rod to flake, respectively. In spite of similar exciton coupling energy in both the aggregates, the flake shaped aggregates undergo a faster exciton relaxation process and the non-radiative relaxation channels are found to depend on the shape of aggregates. The fundamental understanding of morphology controlled ultrafast relaxation processes of aggregated porphyrin is important for designing efficient light harvesting devices.

Solvent-dependent photochemical dynamics of a phenoxazine-based photoredox catalyst

Abstract Organic substitutes for ruthenium and iridium complexes are increasingly finding applications in chemical syntheses involving photoredox catalysis. However, the performance of these organic compounds as electron-transfer photocatalysts depends on their accessible photochemical pathways and excited state lifetimes. Here, the UV-induced dynamics of N-phenyl phenoxazine, chosen as a prototypical N-aryl phenoxazine organic photoredox catalyst, are explored in three solvents, N,N-dimethyl formamide, dichloromethane and toluene, using ultrafast transient absorption spectroscopy. Quantum chemistry calculations reveal the locally excited or charge-transfer electronic character of the excited states, and are used to assign the transient electronic and vibrational bands observed. In toluene-d8, complete ground-state recovery is (31 ± 3) % by internal conversion (IC) from the photo-excited state (or from S1 after IC but before complete vibrational relaxation), (13 ± 2) % via direct decay from vibrationally relaxed S1 (most likely radiative decay, with an estimated radiative lifetime of 13 ns) and (56 ± 3) % via the T1 state (with intersystem crossing (ISC) rate coefficient k ISC = (3.3 ± 0.2) × 108 s−1). In dichloromethane, we find evidence for excited state N-phenyl phenoxazine reaction with the solvent. Excited state lifetimes, ISC rates, and ground-state recovery show only modest variation with changes to the solvent environment because of the locally excited character of the S1 and T1 states.

On Anomalous Fluorescence of Symmetrical Polymethine Dyes

The group-theoretical analysis of polymethine dyes (PMD) showed that relaxation processes between the states S3 and S1 are forbidden, either by radiation or by internal conversion. From the state S3, only transition to the ground state of the molecule is possible. Since the experimental data state that the quantum yield of S3 ⟶ S0 fluorescence does not exceed 1%, it is indicated that the internal conversion rate can be 2 orders of magnitude higher than the radiative relaxation rate of the molecule. Concerning the reasons for the appearance of fluorescence from the higher excited states of molecules, it can be asserted that the necessary condition for the appearance of S3 ⟶ S0 fluorescence is the absence of S0 ⟶ S1(v)-absorption in the region of the S0 ⟶ S3 transition. The sufficient condition is the corresponding symmetry of the excited states, which imposes a prohibition on the S3 ⟶ S1 relaxation process.

Intersystem crossing in tunneling regime: T1 → S0 relaxation in thiophosgene.

The T1 excited state relaxation in thiophosgene has attracted much attention as a relatively simple model for the intersystem crossing (ISC) transitions in polyatomic molecules. The very short (20-40 ps) T1 lifetime predicted in several theoretical studies strongly disagrees with the experimental values (∼20 ns) indicating that the kinetics of T1 → S0 ISC is not well understood. We use the nonadiabatic transition state theory (NA-TST) with the Zhu-Nakamura transition probability and the multireference perturbation theory (CASPT2) to show that the T1 → S0 ISC occurs in the quantum tunneling regime. We also introduce a new zero-point vibrational energy correction scheme that improves the accuracy of the predicted ISC rate constants at low internal energies. The predicted lifetimes of the T1 vibrational states are between one and two orders of magnitude larger than the experimental values. This overestimation is attributed to the multidimensional nature of quantum tunneling that facilitates ISC transitions along the non-minimum energy path and is not accounted for in the one-dimensional NA-TST.

Singlet Fission from Upper Excited Electronic States of Cofacial Perylene Dimer.

Singlet fission directly from the upper excited vibrational and electronic states of cofacial perylene dimers, bypassing the relaxed state S1, was detected within 50 fs. This process competes well with vibrational cooling in S1 (4.7-7.0 ps) and S2 → S1 internal conversion (380 fs). The singlet fission has the energy threshold E = 3.06 eV. Other competitive relaxation processes are excimer and dimer cation formation on an ultrafast time scale. Excitation to higher energy levels (4.96 eV) leads to a higher efficiency of singlet fission.

Ultrafast Dynamics of Encapsulated Molecules Reveals New Insight on the Photoisomerization Mechanism for Azobenzenes.

Spatial confinement can have a profound impact on the dynamics of chemical reactions, especially for isomerization reactions that involve large-amplitude structural rearrangement of a molecule. This work uses ultrafast spectroscopy to probe the effects of confinement on trans → cis photoisomerization following ππ* excitation of 4-propyl stilbene and 4-propyl azobenzene encapsulated in a supramolecular host-guest complex. Transient absorption spectroscopy of the encapsulated azobenzene derivative reveals the formation of two distinct excited-state species with spectral signatures resembling the cis and trans isomers. Formation of the cis species indicates a direct excited-state isomerization channel that is not observed in cyclohexane solution. Comparison with the stilbene analogue suggests that this "hot" excited-state isomerization pathway for encapsulated azobenzene involves primarily in-plane inversion, whereas a 10-fold increase of the excited-state lifetime for the trans isomer suggests that crowding in the capsule hinders isomerization from the relaxed S1 geometry of the trans isomer. This work provides new mechanistic insight on the relative roles of inversion and rotation in the ultrafast photoisomerization of azobenzene derivatives.