Tuning the organic microcrystal laser wavelength of ESIPT-active compounds <i>via</i> controlling the excited enol* and keto* emissions

Li, Jinbiao; Wu, Yishi; Xu, Zhenzhen; Liao, Qing; Zhang, Haihua; Zhang, Yi; Xiao, Lü; Yao, Jiannian; Fu, Hongbing

doi:10.1039/c7tc04207h

Cited by 43 publications

(34 citation statements)

References 31 publications

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“…Another interesting feature that some of these dyes present is so-called dual emission, in other words, the ability to simultaneously emit from two different conformers/tautomers (in two different spectral ranges). ESIPT dyes are particularly promising candidates for medicine [40,55,56], fluorescent probes [57][58][59], molecular logic gates [60][61][62], chemical sensors [63][64][65], photostabilizers [66][67][68], laser dyes [69][70][71][72] and white light-emitting material [73][74][75][76] applications, since they are characterized by unusually large Stokes shifts (exceeding even 5000 cm −1 ). This is indeed an extremely desirable feature for fluorescent dyes, as it leads to negligible overlapping of absorption and emission spectra, which in turn, prevents the emitted photons from being reabsorbed, a phenomenon that often plagues the applications of emissive dyes in biological media as well as in materials.…”

Section: Introductionmentioning

confidence: 99%

Benchmarking Density Functional Approximations for Excited-State Properties of Fluorescent Dyes

Grabarz

Ośmiałowski

2021

Molecules

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This study presents an extensive analysis of the predictive power of time-dependent density functional theory in determining the excited-state properties of two groups of important fluorescent dyes, difluoroboranes and hydroxyphenylimidazo[1,2-a]pyridine derivatives. To ensure statistically meaningful results, the data set is comprised of 85 molecules manifesting diverse photophysical properties. The vertical excitation energies and dipole moments (in the electronic ground and excited states) of the aforementioned dyes were determined using the RI-CC2 method (reference) and with 18 density functional approximations (DFA). The set encompasses DFAs with varying amounts of exact exchange energy (EEX): from 0% (e.g., SVWN, BLYP), through a medium (e.g., TPSSh, B3LYP), up to a major contribution of EEX (e.g., BMK, MN15). It also includes range-separated hybrids (CAM-B3LYP, LC-BLYP). Similar error profiles of vertical energy were obtained for both dye groups, although the errors related to hydroxyphenylimidazopiridines are significantly larger. Overall, functionals including 40–55% of EEX (SOGGA11-X, BMK, M06-2X) ensure satisfactory agreement with the reference vertical excitation energies obtained using the RI-CC2 method; however, MN15 significantly outperforms them, providing a mean absolute error of merely 0.04 eV together with a very high correlation coefficient (R2 = 0.98). Within the investigated set of functionals, there is no single functional that would equally accurately determine ground- and excited-state dipole moments of difluoroboranes and hydroxyphenylimidazopiridine derivatives. Depending on the chosen set of dyes, the most accurate μGS predictions were delivered by MN15 incorporating a major EEX contribution (difluoroboranes) and by PBE0 containing a minor EEX fraction (hydroxyphenylimidazopiridines). Reverse trends are observed for μES, i.e., for difluoroboranes the best results were obtained with functionals including a minor fraction of EEX, specifically PBE0, while in the case of hydroxyphenylimidazopiridines, much more accurate predictions were provided by functionals incorporating a major EEX contribution (BMK, MN15).

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Section: Introductionmentioning

confidence: 99%

Benchmarking Density Functional Approximations for Excited-State Properties of Fluorescent Dyes

Grabarz

Ośmiałowski

2021

Molecules

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“…The requisite of chemical structures for ESIPT is the presence of an intramolecular hydrogen bond (H‐bond) between the proton donor (OH and NH 2 ) and the proton acceptor (N and CO) groups close to one another in a single molecule. Recent notable reports on the ESIPT fluorophores include the polymorph‐dependent emissive crystals, double proton transfer process with an extra‐large Stokes shift, amplified spontaneous emission, lasing system, environment‐sensitive multicolored materials, and the use as emitters with electrically generated intramolecular proton transfers . Most of ESIPT molecules show significant fluorescence in the solid states, not suffering from “concentration quenching” and thus serving as aggregation‐induced emission enhancement (AIEE) materials .…”

Section: Introductionmentioning

confidence: 99%

Highly Fluorescent Liquid Crystals from Excited‐State Intramolecular Proton Transfer Molecules

Zhang

Sakurai

Aotani

et al. 2018

Advanced Optical Materials

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solid-state emitters, electroluminescent devices, organic lasers, and so on. [1][2][3][4][5] Particularly, emission through excitedstate intramolecular proton transfer (ESIPT) mechanism with an extremely large Stokes shift [6][7][8][9] (anti-Kasha rule) suppresses excitation energy dissipation via self-absorption, providing attractive material platforms for optical device fabrication. [10,11] ESIPT is a photochemical process that produces a tautomer with a different electronic structure from the original excited form (Figure 1a). The requisite of chemical structures for ESIPT is the presence of an intramolecular hydrogen bond (H-bond) between the proton donor (OH and NH 2 ) and the proton acceptor (N and CO) groups close to one another in a single molecule. Recent notable reports on the ESIPT fluorophores include the polymorph-dependent emissive crystals, [12,13] double proton transfer process with an extra-large Stokes shift, [14] amplified spontaneous emission, [15][16][17] lasing system, [18][19][20] environment-sensitive multicolored materials, [21][22][23][24] and the use as emitters with electrically generated intramolecular proton transfers. [25] Most of ESIPT molecules show significant fluorescence in the solid states, not suffering from "concentration quenching" and thus serving as aggregation-induced emission enhancement (AIEE) materials. [26][27][28] The ESIPT process requires structural relaxations upon proton transfer, and thus a certain conformational freedom is allowed for the molecular structures. [29] The conformational freedom results in allowing the possible nonradiative pathways especially in solution (Figure 1b), giving AIEE characters to the ESIPT molecules. [30,31] The AIEE character is advantageous because light outputs from the systems are extremely high embedded into actual devices to avoid the concentration quenching. [32] However, most of the previous ESIPT as well as AIEE systems have been mostly reported in the rigid solid phase such as single crystals, polycrystals, or powders [11,12] -not in liquid crystals (LCs). Although columnar LCs with ESIPT-active cores were reported, [33,34] simple rod-shaped LC molecules embedded with ESIPT-active group have been limited. [35,36] In contrast to columnar and cubic liquid crystal phases with highly ordered structures, nematic as well as several smectic subphases can easily align macroscopically by rubbed surfaces, mechanical stimuli, and electric and magnetic fields. [37][38][39] Fluorescence via excited-state intramolecular proton transfer (ESIPT) provides strong light emission with a large Stokes shift and environment-sensitive unique spectral patterns. Particular systems including 2-(2-hydroxyphenyl) benzothiazole (HBT) serve as efficient solid-state emitters with the ESIPT mechanism and aggregation-induced emission enhancement (AIEE) property, but have not been used for liquid crystalline (LC) materials. Here, rod-shaped fluorescent LCs with ESIPT characters are newly developed based on the HBT motif. The design of the targeted mole...

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“…[28][29][30][31][32][33] Chalcone-based compounds, comprising an aromatic ketone and enone system, have found application in both technological and biological settings. [33][34][35][36][37][38][39][40][41][42][43][44][45][46][47][48] The lasing prop- 1. [49][50][51] All reported quantum yields were obtained for single crystals, consequently the effect of trapping as a source of loss of efficiency can be ruled out.…”

Section: Introductionmentioning

confidence: 99%

Molecular and crystalline requirements for solid state fluorescence exploiting excited state intramolecular proton transfer

et al. 2020

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Tuning the organic microcrystal laser wavelength of ESIPT-active compounds via controlling the excited enol* and keto* emissions

Abstract: We tuned the solid-state luminescence of ESIPT-active compounds by controlling the excited keto* and enol* emissions.

Cited by 43 publications

References 31 publications

Benchmarking Density Functional Approximations for Excited-State Properties of Fluorescent Dyes

Benchmarking Density Functional Approximations for Excited-State Properties of Fluorescent Dyes

Highly Fluorescent Liquid Crystals from Excited‐State Intramolecular Proton Transfer Molecules

Molecular and crystalline requirements for solid state fluorescence exploiting excited state intramolecular proton transfer

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