Picosecond time-resolved absorption spectrum measurements of the higher excited singlet state of diphenylacetylene in the solution phase

Hirata, Yoshihiro; Okada, Tadashi; Mataga, Noboru; Nomoto, Tateo

doi:10.1021/j100195a011

Cited by 100 publications

(188 citation statements)

References 2 publications

(3 reference statements)

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“…In the previous paper [1], we confirmed that the fluorescence state of DPA is the S2 state and the S1 state does not emit fluorescence. The strong temperature dependence of the S2 -> S1 internal conversion was demonstrated by using picosecond transient absorption measurement techniques [1].…”

Section: Introductionsupporting

confidence: 77%

“…From the temperature dependence measurements of DM-DPA in n-hexane, we obtained the frequency factor and activation energy of the S2 --> S1 internal conversion to be 6.8 x 10 12 s-1 and 830 cm -1 , respectively, which were similar to those of MO-DPA and DPA [1,3,5]. The vibrational level density should significantly increase with the introduction of methoxy groups, but the methoxy substitution hardly affected the frequency factor and activation energy of the S2 → S1…”

Section: Discussionsupporting

confidence: 52%

“…The strong temperature dependence of the S2 -> S1 internal conversion was demonstrated by using picosecond transient absorption measurement techniques [1]. The questions arisen here are why the internal conversion of DPA between the close lying electronic states is such a slow process and what is the origin of the activation energy.…”

Section: Introductionmentioning

confidence: 87%

“…The details of this system were described elsewhere [1]. The sample was excited with second harmonic of a rhodamine-6G (295 nm) laser and a transient absorption spectrum between 380 and 980 nm was measured by using a picosecond white light generated in Η 2 O/D2 O mixture.…”

Section: Methodsmentioning

confidence: 99%

“…The level inversion of the lowest excited singlet states of dicyano-diphenylbutadiyne was observed. The thermally activated S2 <-S1 internal conversion was not negligible and the sum of the rate constants of 52 → S1 and S2 ←S1 internal conversions was estimated to be about Recently, characters of the low lying excited singlet states of diphenylacetylene (DPA) and its derivatives have been studied in the solution phase [1][2][3][4][5][6][7]. The absorption band of DPA observed at 290 mn was assigned to the 1B1u state, while the lowest excited singlet state was predicted to be 2 1Αg state [8].…”

mentioning

confidence: 99%

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Photophysical Properties of Diphenylacetylene and Diphenylbutadiyne Derivatives in Solution Phase

1998

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By using the femtosecond and picosecond transient absorption measurement techniques, we have investigated diphenylatetylene, diphenylbutadiyne, and their methoxy and cyano derivatives in the solution phase.Both the rapid S2 → S1 internal conversion in the subpicosecond time scale and the triplet formation in the tens of picosecond region were observed for diphenylbutadiyne and its methoxy derivatives, while the dynamic behavior of dimethoxy-diphenylacetylene was quite similar to that of diphenylacetylene. The level inversion of the lowest excited singlet states of dicyano-diphenylbutadiyne was observed. The thermally activated S2 <-S1 internal conversion was not negligible and the sum of the rate constants of 52 → S1 and S2 ←S1 internal conversions was estimated to be about Recently, characters of the low lying excited singlet states of diphenylacetylene (DPA) and its derivatives have been studied in the solution phase [1][2][3][4][5][6][7]. The absorption band of DPA observed at 290 mn was assigned to the 1B1u state, while the lowest excited singlet state was predicted to be 2 1Αg state [8]. Recent INDO/S calculation predicted that the S1 state has Au symmetry [6]. Under the supersonic beam conditions, the energy gap between the 1Β1u and 2 1Αg states is less *The results of this paper were initially presented at

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Section: Introductionsupporting

confidence: 77%

Section: Discussionsupporting

confidence: 52%

Section: Introductionmentioning

confidence: 87%

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 99%

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Photophysical Properties of Diphenylacetylene and Diphenylbutadiyne Derivatives in Solution Phase

1998

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Long‐Range Charge Transportation Induced Organic Host–Guest Dual Color Long Persistent Luminescence

Huang

Deng

Pang

et al. 2021

Advanced Optical Materials

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Long persistent luminescence (LPL) can store light energy in excited states and gradually release it as light. Organic host–guest systems provide a good platform for LPL, and single‐color LPL is often achieved while multicolor LPL is challengeable. Here host–guest supramolecular complexes are presented with dual LPL emissions: thermally activated delayed fluorescence (TADF) (≥100 ms) and room temperature phosphorescence (RTP). A space charge transfer from α‐cyclodextrin to diphenylacetylene (DPA) with long‐range transportation (2.32 mm) carrier along DPA strand in the supramolecular complexes is attributed to generate the TADF and RTP. Fortunately, these supramolecular complexes are readily fabricated from α‐cyclodextrin and DPA or DPA derivatives. The gradient color is observed after removing UV excitation. Furthermore, the hydrophobic property inside α‐cyclodextrin makes the LPL appear by water shedding and disappear by organic solvent infiltration, showing the character of a “switch.” This host–guest space charge transfer strategy paves a way to design LPL materials.

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Excited‐State Intramolecular Charge‐Transfer Dynamics in 4‐Dimethylamino‐4′‐cyanodiphenylacetylene: An Ultrafast Raman Loss Spectroscopic Perspective

et al. 2022

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Photo-initiated intramolecular charge transfer (ICT) processes play a pivotal role in the excited state reaction dynamics in donor-bridge-acceptor systems. The efficacy of such a process can be improved by modifying the extent of π-conjugation, relative orientation/twists of the donor/acceptor entities and polarity of the environment. Herein, 4-dimethylamino-4'-cyanodiphenylacetylene (DACN-DPA), a typical donor-π-bridge-acceptor system, was chosen to unravel the role of various internal coordinates that govern the extent of photo-initiated ICT dynamics. Transient absorption (TA) spectra of DACN-DPA in n-hexane exhibit a lifetime of > 2 ns indicating the formation of a triplet state while, in acetonitrile, a short time-constant of ~2 ps indicates the formation of charge transferred species. Ultrafast Raman loss spectroscopy (URLS) measurements show distinct temporal and spectral dynamics of Raman bands associated with C�C and C=C stretching vibrations. The appearance of a new band at ~1492 cm À 1 in acetonitrile clearly indicates structural modification during the ultrafast ICT process. Furthermore, these observations are supported by TD-DFT computations.

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Picosecond time-resolved absorption spectrum measurements of the higher excited singlet state of diphenylacetylene in the solution phase

Cited by 100 publications

References 2 publications

Photophysical Properties of Diphenylacetylene and Diphenylbutadiyne Derivatives in Solution Phase

Photophysical Properties of Diphenylacetylene and Diphenylbutadiyne Derivatives in Solution Phase

Long‐Range Charge Transportation Induced Organic Host–Guest Dual Color Long Persistent Luminescence

Excited‐State Intramolecular Charge‐Transfer Dynamics in 4‐Dimethylamino‐4′‐cyanodiphenylacetylene: An Ultrafast Raman Loss Spectroscopic Perspective

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