Understanding the Impact of Symmetrical Substitution on the Photodynamics of Sinapate Esters Using Gas-Phase Ultrafast Spectroscopy

Two model biomimetic systems, ethyl sinapate (ES) and its symmetrical analogue, diethyl 2-(4-hydroxy-3,5-dimethoxybenzylidene)malonate (or diethyl sinapate, DES), are stripped to their core fundamentals through gas-phase spectroscopy to understand the underlying photophysics of photothermal materials. Following photoexcitation to the optically bright S1(ππ*) state, DES is found to repopulate the electronic ground state over three orders of magnitude quicker than its non-symmetrical counterpart, ES. Our XMS-CASPT2 calculations shed light on the experimental results, revealing crucial differences in the potential energy surfaces and conical intersection topography between ES and DES. From this work, a peak conical intersection, seen for DES, shows vital importance for the non-radiative ground state recovery of photothermal materials. This fundamental comparative study highlights the potential impact that symmetrical substitution can have on the photodynamics of sinapate esters, providing a blueprint for future advancement in photothermal technology

Implications of flexible spacer rotational processes on the liquid crystal behavior of 4,5-dihydroisoxazole benzoate dimers

The synthesis of some novel non-symmetric liquid crystal dimers, {3-[4-(octyloxyphenyl)]-4,5-dihydroisoxazol-5-yl}alkyl 4-(decyloxy)benzoates (5a–d) and 4-{3-[4-(octyloxyphenyl)]-4,5-dihydroisoxazol-5-yl}alkyl 4-{[6-(octyloxy)naphthalen-2-yl]ethynyl}benzoate (9a–d), are reported. The liquid-crystalline properties, theoretical calculations based on the conformational aspects of the flexible alkyl spacer and X-ray experiments are discussed. The syntheses of the key intermediates, 2-{3-[4-(octyloxy)phenyl]-4,5-dihydroisoxazol-5-yl}alkanol (3a–d), presenting the flexible alkyl spacer were achieved through [3+2] cycloaddition reactions between nitrile oxides, which were generated in situ by oxidation of the respective aromatic oximes, and dipolarophile alkenols (CH2[double bond, length as m-dash]CH(CH2)nOH, n = 1, 2, 3, and 4). The benzoates 5a–d were synthesized through esterification of 3a–d and p-n-decyloxybenzoic acid (4). The esters 9a–d were synthesized through derivatization of isoxazolines 3a–d into 4-{3-[4-(octyloxyphenyl)]-4,5-dihydroisoxazol-5-yl}alkyl 4-bromobenzoate (7a–d) followed by a Sonogashira reaction with 2-ethynyl-6-octyloxynaphthalene (8). 5a and 5b showed a monotropic smectic C phase. 9a/c displayed a enantiotropic nematic (N) mesophase, whereas 9b/d showed a monotropic nematic mesophase. No mesophase was observed for 7a–d. An odd–even effect was observed for 5a–d and 9a–d associated with the crystal to isotropic phase transition and crystal to nematic phase, respectively, as the length of the spacer was increased from 1 to 4 carbon atoms. The transitional properties were higher for odd-numbered members (n = 1 and 3) for all of the series studied. The X-ray data of compounds 5a and 5b are in agreement with polarizing optical microscopy observations with the assignment of an SmC mesophase. Density functional theory calculations using the B3LYP hybrid functional with the level 6-311G(d,p) basis set were performed for molecules 5a–d to correlate the conformation of the flexible spacer and the transitional properties. The conformational analysis showed that the most stable conformation for 5a–d is one where all of the carbon atoms of the flexible spacer are orientated at 180° (antiperiplanar orientation) except for 5a because the spacer is too short. The odd-numbered members have a more bent shape and are less elongated molecules than the even-numbered members. Thus, mesomorphic behavior is dictated by the conformational constraint imposed by the flexible spacer on the mesogenic groups

Direct structural observation of ultrafast photoisomerization dynamics in sinapate esters

Sinapate esters have been extensively studied for their potential application in ‘nature-inspired’ photoprotection. There is general consensus that the relaxation mechanism of sinapate esters following photoexcitation with ultraviolet radiation is mediated by geometric isomerization. This has been largely inferred through indirect studies involving transient electronic absorption spectroscopy in conjunction with steady-state spectroscopies. However, to-date, there is no direct experimental evidence tracking the formation of the photoisomer in real-time. Using transient vibrational absorption spectroscopy, we report on the direct structural changes that occur upon photoexcitation, resulting in the photoisomer formation. Our mechanistic analysis predicts that, from the photoprepared ππ* state, internal conversion takes place through a conical intersection (CI) near the geometry of the initial isomer. Our calculations suggest that different CI topographies at relevant points on the seam of intersection may influence the isomerization yield. Altogether, we provide compelling evidence suggesting that a sinapate ester’s geometric isomerization can be a more complex dynamical process than originally thought

New generation UV-A filters : understanding their photodynamics on a human skin mimic

The sparsity of efficient commercial ultraviolet-A (UV-A) filters is a major challenge toward developing effective broadband sunscreens with minimal human- and eco-toxicity. To combat this, we have designed a new class of Meldrum-based phenolic UV-A filters. We explore the ultrafast photodynamics of coumaryl Meldrum, CMe, and sinapyl Meldrum (SMe), both in an industry-standard emollient and on a synthetic skin mimic, using femtosecond transient electronic and vibrational absorption spectroscopies and computational simulations. Upon photoexcitation to the lowest excited singlet state (S1), these Meldrum-based phenolics undergo fast and efficient nonradiative decay to repopulate the electronic ground state (S0). We propose an initial ultrafast twisted intramolecular charge-transfer mechanism as these systems evolve out of the Franck–Condon region toward an S1/S0 conical intersection, followed by internal conversion to S0 and subsequent vibrational cooling. Importantly, we correlate these findings to their long-term photostability upon irradiation with a solar simulator and conclude that these molecules surpass the basic requirements of an industry-standard UV filter

Towards developing novel and sustainable molecular light-to-heat converters

Light-to-heat conversion materials generate great interest due to their widespread applications, notable exemplars being solar energy harvesting and photoprotection. Another more recently identified potential application for such materials is in molecular heaters for agriculture, whose function is to protect crops from extreme cold weather and extend both the growing season and the geographic areas capable of supporting growth, all of which could help reduce food security challenges. To address this demand, a new series of phenolic-based barbituric absorbers of ultraviolet (UV) radiation has been designed and synthesised in a sustainable manner. The photophysics of these molecules has been studied in solution using femtosecond transient electronic and vibrational absorption spectroscopies, allied with computational simulations and their potential toxicity assessed by in silico studies. Following photoexcitation to the lowest singlet excited state, these barbituric absorbers repopulate the electronic ground state with high fidelity on an ultrafast time scale (within a few picoseconds). The energy relaxation pathway includes a twisted intramolecular charge-transfer state as the system evolves out of the Franck–Condon region, internal conversion to the ground electronic state, and subsequent vibrational cooling. These barbituric absorbers display promising light-to-heat conversion capabilities, are predicted to be non-toxic, and demand further study within neighbouring application-based fields

Mechanistic Aspects of the Photophysics of UVA Filters Based on Meldrum Derivatives

International audienceSkin photoprotection against UVA radiation is crucial, but it is hindered by the sparsity of approved commercial UVA filters. Sinapoyl malate (SM) derivatives are promising candidates for a new class of UVA filters. They have been previously identified as an efficient photoprotective sunscreen in plants due to their fast nonradiative energy dissipation. Combining experimental and computational results, in our previous letter (J. Phys. Chem. Lett. 2021, 12, 337−344) we showed that coumaryl Meldrum (CMe) and sinapoyl Meldrum (SMe) are outstanding candidates for UVA filters in sunscreen formulations. Here, we deliver a comprehensive computational characterization of the excitedstate dynamics of these molecules. Using reaction pathways and excited-state dynamics simulations, we could elucidate the photodeactivation mechanism of these molecules. Upon photoexcitation, they follow a two-step logistic decay. First, an ultrafast and efficient relaxation stabilizes the excited state alongside a 90°twisting around the allylic double bond, giving rise to a minimum with a twisted intramolecular excitedstate (TICT) character. From this minimum, internal conversion to the ground state occurs after overcoming a 0.2 eV barrier. Minor differences in the nonradiative decay and fluorescence of CMe and SMe are associated with an additional minimum present only in the latter

Understanding the Impact of Symmetrical Substitution on the Photodynamics of Sinapate Esters Using Gas-Phase Ultrafast Spectroscopy

Two model biomimetic systems, ethyl sinapate (ES) and its symmetrical analogue, diethyl 2-(4-hydroxy-3,5-dimethoxybenzylidene)malonate (or diethyl sinapate, DES), are stripped to their core fundamentals through gas-phase spectroscopy to understand the underlying photophysics of photothermal materials. Following photoexcitation to the optically bright S 1 (ππ*) state, DES is found to repopulate the electronic ground state over 3 orders of magnitude quicker than its nonsymmetrical counterpart, ES. Our XMS-CASPT2 calculations shed light on the experimental results, revealing crucial differences in the potential energy surfaces and conical intersection topography between ES and DES. From this work, a peaked conical intersection, seen for DES, shows vital importance for the nonradiative ground-state recovery of photothermal materials. This fundamental comparative study highlights the potential impact that symmetrical substitution can have on the photodynamics of sinapate esters, providing a blueprint for future advancement in photothermal technology

Using diketopyrrolopyrroles to stabilize double excitation and control internal conversion

Diketopyrrolopyrrole (DPP) is a pivotal functional group to tune the physicochemical properties of novel organic photoelectronic materials. Among its multiple uses, DPP-thiophene derivatives forming a dimer through a vinyl linker were recently shown to quench the fluorescence observed in their isolated monomers. Here, we explain this fluorescence quenching using computational chemistry. The DPP-thiophene dimer has a low-lying doubly excited state that is not energetically accessible for the monomer. This state delays the fluorescence allowing internal conversion to occur first. We characterize the doubly excited state wavefunction by systematically changing the derivatives to tune the pi-scaffold size and the acceptor and donor characters. The origin of this state\u27s stabilization is related to the increase in the π-system and not to the charge-transfer features. This analysis delivers core conceptual information on the electronic properties of organic chromophores arranged symmetrically around a vinyl linker, opening new ways to control the balance between luminescence and internal conversion

Recommendations for Velocity Adjustment in Surface Hopping

International audienceThis study investigates velocity adjustment directions after hoppings in surface hopping dynamics. Using fulvene and a protonated Schiff base (PSB4) as case studies, we investigate the population decay and reaction yields of different sets of dynamics with the velocity adjusted either in the nonadiabatic coupling, gradient difference, or momentum directions. For the latter, besides the conventional algorithm, we investigated the performance of a reduced kinetic energy reservoir approach recently proposed. Our evaluation also considered velocity adjustment in the directions of approximate nonadiabatic coupling vectors. While results for fulvene are susceptible to the adjustment approach, PSB4 is not. We correlated this dependence to the topography near the conical intersections. When nonadiabatic coupling vectors are unavailable, the gradient difference direction is the best adjustment option. If the gradient difference is also unavailable, a semiempirical vector direction or the momentum direction with a reduced kinetic energy reservoir becomes an excellent option to prevent an artificial excess of back hoppings. The precise velocity adjustment direction is less crucial for describing the nonadiabatic dynamics than the kinetic energy reservoir's size