Ultrafast unidirectional chiral rotation in the <i>Z</i>–<i>E</i> photoisomerization of two azoheteroarene photoswitches

Pang, Xiaojuan; Jiang, Chenwei; Qi, Yongnan; Yuan, Ling; Da, Hu; Zhang, Xiu-Xing; Zhao, Dongfeng; Wang, Dongdong; Lan, Zhenggang; Li, Fuli

doi:10.1039/c8cp04762f

Cited by 14 publications

(18 citation statements)

References 68 publications

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“…We chose this CNNC metric as a result of 1 – 2 a having no particular preference towards a clockwise or counterclockwise rotation about the CNNC dihedral, which results in a similar distribution of positive and negative CNNC dihedral angles. This is in contrast to some reported heteroarenes featuring a stereospecific relaxation mechanism [49, 50] . In 1 – 2 a , the relaxation from the ππ* to the nπ* state occurs at flat geometries similar to the E ‐isomer minimum (see gray circles).…”

Section: Resultscontrasting

confidence: 82%

“…Figure 3s hows the structure at which state crossings occur based on the two main variables:t he CNN angle and the CNNC torsionm easureda st he deviation from planarity (i.e., j CNNCÀ180 j .W ec hose this CNNC metric as ar esult of 1-2a having no particular preference towards ac lockwise or counterclockwise rotation about the CNNC dihedral, which results in as imilard istribution of positive and negative CNNC dihedral angles.T his is in contrast to some reported heteroarenes featuring as tereospecific relaxation mechanism. [49,50] In 1-2a,t he relaxation from the pp*t ot he np*s tate occurs at flat geometries similart ot he E-isomer minimum (see gray circles). As mentioned before, flat geometries have been invoked to explain the ultrafast pp*!np*d ecay in AB.…”

Section: Resultsmentioning

confidence: 98%

“…This is in contrast to some reported heteroarenes featuring a stereospecific relaxation mechanism. [49,50] In 1-2 a, the relaxation from the pp* to the np* state occurs at flat geometries similar to the E-isomer minimum (see gray circles). As mentioned before, flat geometries have been invoked to explain the ultrafast pp*!np* decay in AB.…”

Section: Resultsmentioning

confidence: 99%

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The Photoisomerization Pathway(s) of Push–Pull Phenylazoheteroarenes**

Vela

Corminbœuf

2020

Chemistry A European J

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Azoheteroarenes are the most recent derivatives targetedt of urtheri mprovet he properties of azo-based photoswitches. Their light-induced mechanism for trans-cis isomerization is assumed to be very similart ot hat of the parent azobenzene. As such, they inherited the controversy about the dominant isomerization pathway (rotationv s. inversion)d epending on the excited state (np*v s. pp*). Althought he controversy seems settledi na zobenzene, the extent to which the same conclusions applyt ot he more structurally diverse family of azoheteroarenes is unclear. Here, by means of non-adiabatic molecular dynamics, the photoisomerization mechanism of three prototypicalp henylazoheteroarenes with increasing push-pull characteri su nraveled. The evolutiono fthe rotational and inversion conical intersection energies, the preferred pathway,a nd the associated kinetics upon both np*a nd pp*e xcitationsc an be linked directlyw ith the push-pull substitution effects. Overall, the working conditions of this family of azo-dyes is clarified and ap ossibility to exploit push-pull substituents to tune their photoisomerizationm echanism is identified, with potentialimpact on their quantum yield. [**] Ap revious versiono ft his manuscript has been deposited on ap reprint server (

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Section: Resultscontrasting

confidence: 82%

Section: Resultsmentioning

confidence: 98%

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The Photoisomerization Pathway(s) of Push–Pull Phenylazoheteroarenes**

Vela

Corminbœuf

2020

Chemistry A European J

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“…All semi-empirical calculations were performed with the OM2/MRCI method as implemented in the development version of the MNDO program [ 30 ]. This method can balance the computational cost and accuracy well, as shown by many benchmark calculations [ 31 , 32 , 33 ], and has been used successfully in many calculations of photoinduced processes [ 34 , 35 , 36 , 37 , 38 , 39 , 40 , 41 , 42 , 43 ]. The required energies, gradients, and nonadiabatic coupling elements were calculated analytically in the geometry optimizations and dynamics simulations.…”

Section: Computational Detailsmentioning

confidence: 99%

Design and Nonadiabatic Photoisomerization Dynamics Study of a Three-Stroke Light-Driven Molecular Rotary Motor

Yang

Zhao

et al. 2022

IJMS

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Working cycle of conventional light-driven molecular rotary motors (LDMRMs), especially Feringa-type motors, usually have four steps, two photoisomerization steps, and two thermal helix inversion (THI) steps. THI steps hinder the ability of the motor to operate at lower temperatures and limit the rotation speed of LDMRMs. A three-stroke LDMRM, 2-(2,7-dimethyl-2,3-dihydro-1H-inden-1-ylidene)-1,2-dihydro-3H-pyrrol-3-one (DDIY), is proposed, which is capable of completing an unidirectional rotation by two photoisomerization steps and one thermal helix inversion step at room temperature. On the basis of trajectory surface-hopping simulation at the semi-empirical OM2/MRCI level, the EP→ZP and ZP→EM nonadiabatic photoisomerization dynamics of DDIY were systematically analyzed. Quantum yields of EP→ZP and ZP→EM photoisomerization of DDIY are ca. 34% and 18%, respectively. Both EP→ZP and ZP→EM photoisomerization processes occur on an ultrafast time scale (ca. 100–300 fs). This three-stroke LDMRM may stimulate further research for the development of new families of more efficient LDMRMs.

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“…[62] This OM2/MRCI method has been used to simulate the nonadiabatic dynamics of organic photochemistry systems comprising the Wolff rearrangement, intermolecular proton transfer (ESIPT), cis-trans isomerization, etc. [63][64][65][66][67][68] In this study, 14 electrons and 14 orbitals were included in the OM2/MRCI calculations (see Figure S2 for the orbitals). Before the nonadiabatic dynamics simulations, a NVT (T = 300 K) ground state dynamics simulation of 5 ps was performed, and the randomly selected samples from the trajectory based on computed S 0 -S 1 transition probabilities were chosen as the initial atomic coordinates for the S 1 state nonadiabatic dynamics simulations.…”

Section: Computational Detailsmentioning

confidence: 99%

Potential‐Energy Surface and Dynamics Simulation of THBDBA: An Annulated Tetraphenylethene Derivative Combining Aggregation‐Induced Emission and Switch Behavior

et al. 2019

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Electronic structure calculations and nonadiabatic dynamics simulations were carried out on the excited state decay mechanism of a typical aggregation-induced emission (AIE)active molecule, 10,10',11,11'-tetrahydro-5,5'-bidibenzo[a,d][7] annulenylidene (THBDBA), which was experimentally found to be almost non-emissive in THF solution but highly luminescent as an aggregate. At the MS-CASPT2//CASSCF level, the decay path from S 1 leads to a conical intersection (CI) seam with the ground state (S 0 ) via a cyclization process of two neighboring phenyl groups. Nonadiabatic dynamics simulations of 367 surface hopping trajectories show that all the structures of hopping points resemble those of the S 1 /S 0 CI seam with cyclized geometry. The final structures of trajectories hopping to S 0 belong to either Franck-Condon (FC) like structures (66.8 %) or cyclized conformers (33.2 %), which agrees well with the experimental result of 23 % cyclization product (Y. Cai et al. Chem. Sci., 2011, 2, 2029-2034. Our results also indicate that long-time irradiation leads to a photostationary state where the open and cyclized forms interconvert photochemically. The preference for photocyclization over double bond isomerization is due to the rigidity of the dihydrofulvene rings. From the point of view of AIE, the calculations suggest that THBDBA follows our restricted access to a CI (RACI) model because the photocyclization requires large displacements of the phenyl rings. These displacements must be blocked in the aggregate phase, inhibiting the decay and leading to luminescence. Our study contributes to understand the AIE and switch behavior of THBDBA and will be useful to support the design of new molecules with these features.[a] Dr.

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Ultrafast unidirectional chiral rotation in the Z–E photoisomerization of two azoheteroarene photoswitches

Abstract: Based on a large number of trajectories starting from the Z-isomer, for both azoheteroarenes, more than 99% of the trajectories decay through conical intersections with the same helicities as their initial geometries.

Cited by 14 publications

References 68 publications

The Photoisomerization Pathway(s) of Push–Pull Phenylazoheteroarenes**

The Photoisomerization Pathway(s) of Push–Pull Phenylazoheteroarenes**

Design and Nonadiabatic Photoisomerization Dynamics Study of a Three-Stroke Light-Driven Molecular Rotary Motor

Potential‐Energy Surface and Dynamics Simulation of THBDBA: An Annulated Tetraphenylethene Derivative Combining Aggregation‐Induced Emission and Switch Behavior

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