Fate of photoexcited trans-aminostilbenes

Yang, Jye‐Shane; Lin, Che‐Jen

doi:10.1016/j.jphotochem.2015.05.031

Cited by 24 publications

(30 citation statements)

References 81 publications

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“…Functionalised charge transfer stilbenes, like 4-dimethylamino-4'-cyanostilbene (DCS), have been studied with experimental 5 and theoretical methods for more than forty years, but there is no general consent concerning the existence and nature of the TICT state. The dual fluorescence phenomenon of DCS can be partially explained by the existence of a TICT state formed by rotation around the C-C anilino bond [ [31][32][33] or the C-N amino bond [ [34][35][36][37], but no evidence for the existence of a TICT state and/or of dual fluorescence has been found in several studies [38][39][40]. Excited state re-absorption of fluorescence has been proposed as a potential alternative to the formation of a TICT state [ 41 ].…”

Section: Introductionmentioning

confidence: 99%

Influence of charge transfer on the isomerisation of stilbene derivatives for application in cancer therapy

Holzmann

Bernasconi

Bisby

et al. 2018

Phys. Chem. Chem. Phys.

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Section: Introductionmentioning

confidence: 99%

Influence of charge transfer on the isomerisation of stilbene derivatives for application in cancer therapy

Holzmann

Bernasconi

Bisby

et al. 2018

Phys. Chem. Chem. Phys.

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“…The CASSCF calculation with full valence active space that consists of all the valence orbitals and electrons for DANS is computationally unaffordable. Therefore, the orbital properties and performance on vertical excitation energy prediction of some common reduced active spaces, such as CAS (10,8), CAS (10,10), CAS (12,12) and CAS (18,12) were investigated, and finally the CAS (18,12) was chosen with consideration of both the computation efficiency and accuracy. Based on the active molecular orbitals of those active spaces for trans-S 0 and cis-S 0 presented in Supplementary Materials Figure S1, it is evident that the corresponding orbitals of CAS (18,12) were in agreement with CAS (10,8) but different from CAS (10,10) and CAS (12,12).…”

Section: Theoretical Methods and Computational Detailsmentioning

confidence: 99%

“…Upon excitation to the S 1 state, both transand cis-stilbene evolve along the C=C torsion coordinate and decay via twisted S 1 /S 0 conical intersections (CIs) [12], while for substituted stilbene, the triplet route mediated by intersystem crossing (ISC) may open [13,14], and the formation of stable intramolecular charge transfer (ICT) states evidently affect the fluorescence efficiency [13][14][15][16][17][18][19]. Therefore, the optical properties of stilbenes can be controlled by introducing suitable substitution groups [8].…”

Section: Introductionmentioning

confidence: 99%

Photorelaxation Pathways of 4-(N,N-Dimethylamino)-4′-nitrostilbene Upon S1 Excitation Revealed by Conical Intersection and Intersystem Crossing Networks

Xue

Lei

et al. 2020

Molecules

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Multi-state n-electron valence state second order perturbation theory (MS-NEVPT2) was utilized to reveal the photorelaxation pathways of 4-(N,N-dimethylamino)-4′-nitrostilbene (DANS) upon S1 excitation. Within the interwoven networks of five S1/S0 and three T2/T1 conical intersections (CIs), and three S1/T2, one S1/T1 and one S0/T1 intersystem crossings (ISCs), those competing nonadiabatic decay pathways play different roles in trans-to-cis and cis-to-trans processes, respectively. After being excited to the Franck–Condon (FC) region of the S1 state, trans-S1-FC firstly encounters an ultrafast conversion to quinoid form. Subsequently, the relaxation mainly proceeds along the triplet pathway, trans-S1-FC → ISC-S1/T2-trans → CI-T2/T1-trans → ISC-S0/T1-twist → trans- or cis-S0. The singlet relaxation pathway mediated by CI-S1/S0-twist-c is hindered by the prominent energy barrier on S1 surface and by the reason that CI-S1/S0-trans and CI-S1/S0-twist-t are both not energetically accessible upon S1 excitation. On the other hand, the cis-S1-FC lies at the top of steeply decreasing potential energy surfaces (PESs) towards the CI-S1/S0-twist-c and CI-S1/S0-DHP regions; therefore, the initial twisting directions of DN and DAP moieties determine the branching ratio between αC=C twisting (cis-S1-FC → CI-S1/S0-twist-c → trans- or cis-S0) and DHP formation relaxation pathways (cis-S1-FC → CI-S1/S0-DHP → DHP-S0) on the S1 surface. Moreover, the DHP formation could also take place via the triplet relaxation pathway, cis-S1-FC → ISC-S1/T1-cis → DHP-T1 → DHP-S0, however, which may be hindered by insufficient spin-orbit coupling (SOC) strength. The other triplet pathways for cis-S1-FC mediated by ISC-S1/T2-cis are negligible due to the energy or geometry incompatibility of possible consecutive stepwise S1 → T2 → T1 or S1 → T2 → S1 processes. The present study reveals photoisomerization dynamic pathways via conical intersection and intersystem crossing networks and provides nice physical insight into experimental investigation of DANS.

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“…Normally, www.chemphotochem.org the TICT state of D-A single-bond torsion is much less fluorescent. [14] The dramatic decrease in the quantum yield of fluorescence from 3.2 %( hexane) to 0.08 %( DCM) to 0.02 %( MeCN) also points to the formation of TICT. Am odified excited-state decay pathway for 5Me-HTI-TPA-R compounds is shown in Scheme 2A,b ased on the literature.…”

mentioning

confidence: 99%

“…Theoretical calculations have already been employed to discuss the electron-density distribution in the excited state of certainc ompounds (such as stilbene [14] and TAAd erivatives [3c] ). The interpretationf or the 5Me-HTI-TPA-R compounds herein should be comparable.…”

mentioning

confidence: 99%

The Effect of Substituent‐Dependent Photoinduced Intramolecular Charge Transfer on the Photochromism of Hemithioindigos

Wang

Rueck‐Braun

2017

ChemPhotoChem

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A series of N,N′‐diarylamine‐modified hemithioindigos (HTIs) were synthesized and characterized. Photochemical Z/E isomerization around the C=C double bond occurred for all novel HTIs in various solvents. Due to a strong donor–acceptor π‐conjugated structure, the novel HTIs exhibited a strong red shift and clear solvatochromism in steady‐state absorption and fluorescence spectroscopic measurements, respectively. An intramolecular charge transfer (ICT) from the diarylamine‐substituted stilbene component (donor) to the thioindigo part (acceptor) strongly affects the isomerization behavior. HTI is the dominating photochromic unit in this system but the substitution pattern on the triarylamine (TAA) moiety causes unusually strong changes in the photostationary states (PSS) and thermal stabilities. Electron‐withdrawing substituents (such as cyano groups) strongly improve thermal stabilities and enrich the E‐isomer content in the photostationary state, however electron‐donating substituents play a converse effect, for example, in the solvents hexane and tetrachloroethene. The low E ratio in the PSS in more polar solvents, such as acetonitrile, can be explained by a very fast thermal back reaction and formation of a new decay state in OMe‐substituted compounds.

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Fate of photoexcited trans-aminostilbenes

Cited by 24 publications

References 81 publications

Influence of charge transfer on the isomerisation of stilbene derivatives for application in cancer therapy

Influence of charge transfer on the isomerisation of stilbene derivatives for application in cancer therapy

Photorelaxation Pathways of 4-(N,N-Dimethylamino)-4′-nitrostilbene Upon S1 Excitation Revealed by Conical Intersection and Intersystem Crossing Networks

The Effect of Substituent‐Dependent Photoinduced Intramolecular Charge Transfer on the Photochromism of Hemithioindigos

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