Photophysical properties of symmetrically substituted diarylacetylenes and diarylbuta-1,3-diynes

Bylińska, Irena; Wierzbicka, Małgorzata; Czaplewski, Cezary; Wiczk, Wiesław

doi:10.1039/c5pp00197h

Cited by 14 publications

(5 citation statements)

References 69 publications

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“…Recently, Xie et al reported aggregation induced WLE from a carbazolyl- and phenothiazinyl-substituted benzophenone . There has been increasing interest in various applications − and photophysics − of butadiynyl derivatives in recent years. In a program aimed at the understanding of photophysics of some small butadiynyl fluorophores, − we observed recently that a donor (−NMe 2 )–acceptor (−CN) substituted diphenylbutadiynyl derivative ( Me 2 NPBPCN ; Figure ) shows the WLE in acetonitrile (CH 3 CN) through a control of locally excited (LE) and exciplex emissions.…”

Section: Introductionmentioning

confidence: 99%

White Light Emission in Butadiyne Bridged Pyrene–Phenyl Hybrid Fluorophore: Understanding the Photophysical Importance of Diyne Spacer and Utilizing the Excited-State Photophysics for Vapor Detection

2016

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Generation of white light emission (WLE) from a single organic fluorophore is challenging because of the need to get fluorescence covering the visible region (400-700 nm) upon excitation of the dye at near-ultraviolet wavelength. Herein, we report WLE from a butadiyne bridged pyrene-phenyl hybrid fluorophore in mixed-aqueous solvents as well as in polymer film matrices. The ability of the butadiynyl dye to emit from multiple excited states such as locally excited (LE; 400-500 nm), aggregate (excimer type; 475-600 nm), and charge transfer (CT; 500-750 nm) states spanning the emission almost throughout the visible range has made the generation of the white light to be possible. In highly polar solvent such as acetonitrile, the butadiynyl dye emits from the LE and CT states, and the WLE is achieved through a control of the dye concentration such that intermolecular CT (exciplex type) contributes along with the intramolecular CT and LE emissions. In mixed-aqueous systems such as water-acetonitrile and water-N,N-dimethylformamide, the CT emission is red-shifted (because of the high dielctric constant of water), and the contribution of the aggregate emission (originated because of the poor solvent water) is important in maintaining the relative distribution of the fluorescence intensities (LE, excimer, and CT) in the entire visible region. The significance of the diyne spacer in achieving the WLE is delineated through a control study with a single acetylenic analogue. The LE, aggregate, and CT emissions are involved in generating bluish-white light in a poly(vinyl alcohol) film matrix of the butadiynyl dye. Blue emission is noted in a poly(methyl methacrylate) (PMMA) film matrix of the dye with a major contribution from the LE and a minor contribution from the aggregate state. Exposure of the PMMA film of the dye to polar aprotic vapors assists in gaining the CT state emission such that the LE, aggregate, CT emissions cover the entire visible region to produce the WLE. This opens a new strategy for selective vapor sensing.

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Section: Introductionmentioning

confidence: 99%

White Light Emission in Butadiyne Bridged Pyrene–Phenyl Hybrid Fluorophore: Understanding the Photophysical Importance of Diyne Spacer and Utilizing the Excited-State Photophysics for Vapor Detection

2016

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“…It is worth noting that perylene compounds substituted at the third position exhibit a bathochromic shift compared to perylenes substituted at the second position. Although aryl residues in diarylacetylenes are coplanar in their ground state, the rotation barrier is very low, and a number of conformations is present in solutions [56][57][58][59][60]. Compounds 3a-c exhibited fluorescence maxima in the 472-476 nm range, while compounds 3d-f showed fluorescence in the 440-442 nm range.…”

Section: Spectral Properties and 1 O2 Generationmentioning

confidence: 99%

Membrane-Targeting Perylenylethynylphenols Inactivate Medically Important Coronaviruses via the Singlet Oxygen Photogeneration Mechanism

Mariewskaya,

Gvozdev,

Chistov

et al. 2023

Molecules

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Perylenylethynyl derivatives have been recognized as broad-spectrum antivirals that target the lipid envelope of enveloped viruses. In this study, we present novel perylenylethynylphenols that exhibit nanomolar or submicromolar antiviral activity against Severe Acute Respiratory Syndrome Coronavirus-2 (SARS-CoV-2) and feline infectious peritonitis virus (FIPV) in vitro. Perylenylethynylphenols incorporate into viral and cellular membranes and block the entry of the virus into the host cell. Furthermore, these compounds demonstrate an ability to generate singlet oxygen when exposed to visible light. The rate of singlet oxygen production is positively correlated with antiviral activity, confirming that the inhibition of fusion is primarily due to singlet-oxygen-induced damage to the viral envelope. The unique combination of a shape that affords affinity to the lipid bilayer and the capacity to generate singlet oxygen makes perylenylethynylphenols highly effective scaffolds against enveloped viruses. The anticoronaviral activity of perylenylethynylphenols is strictly light-dependent and disappears in the absence of daylight (under red light). Moreover, these compounds exhibit negligible cytotoxicity, highlighting their significant potential for further exploration of the precise antiviral mechanism and the broader scope and limitations of this compound class.

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“…It is important to note that the πσ* state in DPA is accessed with a vibronic coupling via low-frequency modes, which results in a dramatic increase of φ PL upon lowering the temperature from 0.002 (300 K) to 0.69 (77 K) . Similarly, DPB with two triple bonds shows temperature-activated nonradiative losses but was predicted to have less weakening in the CC bond than DPA. , In contrast, a large excess energy was estimated to achieve a σπ*/ππ* state intersection in DNB, which suggests that larger naphthyl end-groups reduce the possibility toward CC bending and thus eliminate transitions to the πσ* state.…”

mentioning

confidence: 99%

“…51 Similarly, DPB with two triple bonds shows temperature-activated nonradiative losses but was predicted to have less weakening in the CC bond than DPA. 52,53 In contrast, a large excess energy was estimated to achieve a σπ*/ ππ* state intersection in DNB, 54 which suggests that larger naphthyl end-groups reduce the possibility toward CC bending and thus eliminate transitions to the πσ* state.…”

mentioning

confidence: 99%

Helical Molecular Orbitals to Induce Spin–Orbit Coupling in Oligoyne-Bridged Bifluorenes

Baronas

Komskis

Tankelevičiu̅tė

et al. 2021

J. Phys. Chem. Lett.

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Singlet−Triplet energy exchange is an area of active research due to its role in optoelectronic devices and photodynamic therapy. Large spin−orbit coupling (SOC) is difficult to achieve in simple hydrocarbon structures limiting the intersystem crossing (ISC) rates. A new approach to enhance the spin−orbit coupling via helical molecular orbitals is investigated in oligoyne-bridged bifluorenes. Transient absorption studies showed a singlet-to-triplet ISC rate of up to 6 ns −1 resulting in 0.84 triplet yield. Density functional calculations revealed a direct relation between high ISC and large SOC values mediated by helical molecular orbitals. Calculations and spectroscopic data also suggested that El-Sayed forbidden ISC occurs as a direct transition between 1 ππ* and 3 ππ*, which becomes allowed due to a symmetry-breaking interaction leading to mixing between orthogonal π-systems in the oligoyne fragment.

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Photophysical properties of symmetrically substituted diarylacetylenes and diarylbuta-1,3-diynes

Cited by 14 publications

References 69 publications

White Light Emission in Butadiyne Bridged Pyrene–Phenyl Hybrid Fluorophore: Understanding the Photophysical Importance of Diyne Spacer and Utilizing the Excited-State Photophysics for Vapor Detection

White Light Emission in Butadiyne Bridged Pyrene–Phenyl Hybrid Fluorophore: Understanding the Photophysical Importance of Diyne Spacer and Utilizing the Excited-State Photophysics for Vapor Detection

Membrane-Targeting Perylenylethynylphenols Inactivate Medically Important Coronaviruses via the Singlet Oxygen Photogeneration Mechanism

Helical Molecular Orbitals to Induce Spin–Orbit Coupling in Oligoyne-Bridged Bifluorenes

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