Molecular-Shape-Dependent Luminescent Behavior of Dye Aggregates: Bent versus Linear Benzocoumarins

Moon, Hyunsoo; Xuan, Qui Pham; Kim, Dokyoung; Kim, Yonghwi; Park, Jae-Woo; Lee, Chong Han; Kim, Hyeongju; Kawamata, Ayano; Park, Soo Young; Ahn, Kyo Han

doi:10.1021/cg501567s

Cited by 39 publications

(27 citation statements)

References 35 publications

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“…Understanding the structure-property relationship is very important to guide the design of correct molecules for their providential applications1617181920212223. Artful molecular design through varying molecular backbone substituent groups and effective π-conjugation lengths or impacting the intra/intermolecular interactions to achieve high emission in the solid state is the most common method2425262728.…”

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confidence: 99%

Anion-controlled dimer distance induced unique solid-state fluorescence of cyano substituted styrene pyridinium

Zhang

Kong

et al. 2016

Sci Rep

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Molecular packing arrangements play a key role in dominating the photophysical properties of luminophores in aggregated state but fine control of the molecular packing is a great challenge. This article describes a unique cyano substituted styrene pyridinium with interesting solid-state fluorescence that can be finely tuned by simple change of counteranions. The dilute solutions of the organic salts (PyCl, PyNO3, PyOTs and PyPh4B) exhibit very weak fluorescence. The crystals of the organic salts (PyCl, PyNO3, and PyOTs) show much enhanced fluorescence compared with their dilute solutions. It is interesting that the emissions changed from bluish-green to deep-blue and fluorescence quantum yields increase from 2.5% to 13.1% with the increasing of steric hindrance of the anions from chloridion, nitrate, to p-toluenesulfonate. Crystal and DFT studies reveal that the enhanced fluorescence is ascribed to the formation of dimers and bigger anions induce larger molecular separation in dimers. Tetraphenylboron anion with very large steric hindrance impedes the formation of dimers and thus results in non-fluorescent salt (PyPh4B). Meanwhile, this unique dimeric packing endows the crystal of PyNO3 with anisotropic fluorescence.

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confidence: 99%

Anion-controlled dimer distance induced unique solid-state fluorescence of cyano substituted styrene pyridinium

Zhang

Kong

et al. 2016

Sci Rep

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“…Effort has been put forward to tune the molecular packing through structural modification and thereby influence the solid state fluorescence output. [23][24][25][26][27][28][29][30][31][32][33][34][35] In this regard, small organic derivatives with olefin, acetylene, phenylenevinylene and phenyleneethynylene spacers have found current interest. 19,24,[36][37][38][39][40] Davis et al reported the solid state fluorescence of alkoxy-cyano substituted diphenylbutadiene derivatives.…”

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confidence: 99%

Contrasting Solid-State Fluorescence of Diynes with Small and Large Aryl Substituents: Crystal Packing Dependence and Stimuli-Responsive Fluorescence Switching

2015

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There has been a significant current interest in solid state luminescence of organic molecules and their stimuli responsive fluorescence switching behavior. Although small organic derivatives with olefinic, acetylenic, phenylenevinylenic, phenyleneethynylenic spacers are widely documented as solid state emitters in the literature, the solid state photophysics of organic derivatives with "butadiyne" spacer still remains unexplored. We provide detailed investigation on the solid state fluorescence properties of a series of butadiynyl fluorophores. Replacement of a phenyl ring, which is at periphery of the butadiyne bridge, with a large moiety such as pyrenyl group furnishes contrasting emissions in the solid state. While the butadiyne bridged phenyl derivatives show a blue shift of emission maxima in the solid powder with respect to monomer spectra in solution state, the butadiyne bridged pyrenyl derivatives exhibit a red shift in the solid state. The blue shift of the emission maxima of the butadiyne bridged phenyl derivatives in the solid powder is attributed to allowed excitonic transition in aggregates with nearly parallel transition dipoles. On the other hand, formation of pyrenyl excimer accounts for the red shift of the butadiyne bridged pyrenyl derivatives in the solid powder. In addition to that, the solid state fluorescence of the pyrenyl analogues is reversibly switched between two aggregate forms through external heating and rubbing stimuli.

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“…In general,a lteration of the molecular structure and its packing modes in the crystal under external stimuli could affect the emission colour and intensity. [24] The solidP Ls pectra of compounds TPEB, TPEF and TPEN were red shifteda nd accompanied by intensity increasing after grinding, whereas for TPECN,t he peak was red shifted and the intensity was just slightly reduceda fter grinding. Compound TPEB exhibited a F F of 12.28 %w ith ap eak at 477 nm.…”

Section: Mechanofluorochromic Luminescence (Mfc)mentioning

confidence: 92%

Molecular Packing‐Controlled Mechanical‐Induced Emission Enhancement of Tetraphenylethene‐Functionalised Pyrazoline Derivatives

Guo

Zhang

Kong

et al. 2020

Chemistry A European J

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Organic mechanofluorochromic (MFC) materials with mechanical‐induced emission enhancement (MIEE) are scarce. Herein, Aggregation‐induced emission (AIE)‐active tetraphenylethene‐functionalised pyrazoline derivatives with various non‐conjugated substituent groups (Br, F, N,N‐dimethylamino and cyano groups for TPEB, TPEF, TPEN and TPECN, respectively) were designed and synthesised. The fluorescence spectra of the compounds in the solid state were sensitive to mechanical stimuli and exhibited unique MFC properties. The solid fluorescence peaks of all compounds were red shifted, whereas the quantum yields of TPEB, TPEF and TPEN were increased and that of TPECN was slightly reduced after grinding. The MIEE mechanism was systematically investigated through structure–property relationship studies. The results showed that the pyrazoline ring of TPEB with MIEE property formed H‐dimer aggregates with weak π–π stacking in the solid state. After grinding, the synergistic effects of conformational planarization and destructive π–π interactions induced the red shift of the fluorescence peak and the intensity enhanced. TPECN formed incompact J‐aggregates with weak intermolecular interactions instead. The conformational planarization and increased intermolecular interactions induced by grinding led to the red‐shifted peak and the slightly reduced intensity. These results clearly demonstrated that the translation of packing arrangements is an efficient method to design MIEE materials, which opens a new scope for designing unique MFC materials.

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Molecular-Shape-Dependent Luminescent Behavior of Dye Aggregates: Bent versus Linear Benzocoumarins

Cited by 39 publications

References 35 publications

Anion-controlled dimer distance induced unique solid-state fluorescence of cyano substituted styrene pyridinium

Anion-controlled dimer distance induced unique solid-state fluorescence of cyano substituted styrene pyridinium

Contrasting Solid-State Fluorescence of Diynes with Small and Large Aryl Substituents: Crystal Packing Dependence and Stimuli-Responsive Fluorescence Switching

Molecular Packing‐Controlled Mechanical‐Induced Emission Enhancement of Tetraphenylethene‐Functionalised Pyrazoline Derivatives

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