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Synthesis, photophysical and electrochemical properties of pyridine, pyrazine and triazine-based (D-?-)₂A fluorescent dyes.

ABSTRACT: The donor-acceptor-?-conjugated (D-?-)₂A fluorescent dyes OUY-2, OUK-2 and OUJ-2 with two (diphenylamino)carbazole thiophene units as D (electron-donating group)-? (?-conjugated bridge) moiety and a pyridine, pyrazine or triazine ring as electron-withdrawing group (electron-accepting group, A) have been designed and synthesized. The photophysical and electrochemical properties of the three dyes were investigated by photoabsorption and fluorescence spectroscopy, Lippert-Mataga plots, cyclic voltammetry and density functional theory calculations. The photoabsorption maximum (?_max,abs) and the fluorescence maximum (?_max,fl) for the intramolecular charge-transfer characteristic band of the (D-?-)₂A fluorescent dyes show bathochromic shifts in the order of OUY-2 < OUK-2 < OUJ-2. Moreover, the photoabsorption bands of the (D-?-)₂A fluorescent dyes are nearly independent of solvent polarity, while the fluorescence bands showed bathochromic shifts with increasing solvent polarity (i.e., positive fluorescence solvatochromism). The Lippert-Mataga plots for OUY-2, OUK-2 and OUJ-2 indicate that the ?? (= ?_e - ?_g) value, which is the difference in the dipole moment of the dye between the excited (?_e) and the ground (?_g) states, increases in the order of OUY-2 < OUK-2 < OUJ-2. Therefore, the fact explains our findings that OUJ-2 shows large bathochromic shifts of the fluorescence maxima in polar solvents, as well as the Stokes shift values of OUJ-2 in polar solvents are much larger than those in nonpolar solvents. The cyclic voltammetry of OUY-2, OUK-2 and OUJ-2 demonstrated that there is little difference in the HOMO energy level among the three dyes, but the LUMO energy levels decrease in the order of OUY-2 > OUK-2 > OUJ-2. Consequently, this work reveals that for the (D-?-)₂A fluorescent dyes OUY-2, OUK-2 and OUJ-2 the bathochromic shifts of ?_max,abs and ?_max,fl and the lowering of the LUMO energy level are dependent on the electron-withdrawing ability of the azine ring, which increases in the order of OUY-2 < OUK-2 < OUJ-2.

SUBMITTER: Imato K

PROVIDER: S-EPMC6664397 | biostudies-literature | 2019

REPOSITORIES: biostudies-literature

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Synthesis, photophysical and electrochemical properties of pyridine, pyrazine and triazine-based (D-π-)2A fluorescent dyes.

Imato Keiichi K Enoki Toshiaki T Uenaka Koji K Ooyama Yousuke Y

Beilstein journal of organic chemistry 20190722

The donor-acceptor-π-conjugated (D-π-)2A fluorescent dyes OUY-2, OUK-2 and OUJ-2 with two (diphenylamino)carbazole thiophene units as D (electron-donating group)-π (π-conjugated bridge) moiety and a pyridine, pyrazine or triazine ring as electron-withdrawing group (electron-accepting group, A) have been designed and synthesized. The photophysical and electrochemical properties of the three dyes were investigated by photoabsorption and fluorescence spectrosc ...[more]

PMID: 31435445

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Project description:Bathochromic or hypsochromic shift-type mechanofluorochromism (b-MFC or h-MFC) was found for (D-π-)2A-type azine-based fluorescent dyes OUY-2, OUK-2, and OUJ-2 possessing intramolecular charge-transfer (ICT) characteristics from two (diphenylamino)carbazole-thiophene units as D (electron-donating group)-π (π-conjugated bridge) moieties to a pyridine, pyrazine, or triazine ring as A (electron-withdrawing group): grinding of the recrystallized dyes induced red or blue shifts of the fluorescent colors, that is, bathochromic or hypsochromic shifts of the fluorescence maximum wavelengths (λfl-solid max). The degrees of MFC evaluated by the absolute value of differences (Δλ fl-solid max) in λfl-solid max before and after grinding of the recrystallized dyes increased in the order of OUY-2 (+7 nm) < OUK-2 (-17 nm) < OUJ-2 (+45 nm), so that OUJ-2 exhibits obvious b-MFC, but OUK-2 exhibits h-MFC. X-ray powder diffraction (XRD) and differential scanning calorimetry (DSC) demonstrated that the recrystallized dyes were in the crystalline state but the ground dyes were in the amorphous state. When the ground solids were heated above their crystallization temperatures (T c), the colors and fluorescent colors recovered to the original ones before grinding or converted to other ones, that is, heating the ground solids in the amorphous state induced the recrystallization to recover the original microcrystals or to form other microcrystals due to polymorph transformation. However, (D-π-)2Ph-type fluorescent dye OTK-2 having a phenyl group as a substitute for the azine rings exhibited non-obvious MFC. Molecular orbital (MO) calculations indicated that the values of the dipole moments (μ g) in the ground state were 4.0 debye, 1.4 debye, 3.2 debye, and 2.9 debye for OTK-2, OUY-2, OUK-2, and OUJ-2, respectively. Consequently, on the basis of experimental results and MO calculations, we have demonstrated that the MFC of the (D-π-)2A-type azine-based fluorescent dyes is attributed to reversible switching between the crystalline state of the recrystallized dyes and the amorphous state of the ground dyes with changes in the intermolecular dipole-dipole and π-π interactions before and after grinding. Moreover, this work reveals that (D-π-)2A fluorescent dyes possessing dipole moments of ca. 3 debye as well as moderate or intense ICT characteristics make it possible to activate the MFC.

Project description:Purpurinimide methyl esters, bearing variable lengths of N-substitutions, were conjugated individually to a cyanine dye with a carboxylic acid functionality. The results obtained from in vitro and in vivo studies showed a significant impact of the linkers joining the phototherapeutic and fluorescence imaging moieties. The photosensitizer-fluorophore conjugate with a PEG linker showed the highest uptake in the liver, whereas the conjugate linked with two carbon units showed excellent tumor-imaging and PDT efficacy at 24 h postinjection. Whole body imaging and biodistribution studies at variable time points portrayed enhanced fluorescent uptake of the conjugates in the tumor compared to that in the skin. Interestingly, the conjugate with the shortest linker and the one joining with two carbon units showed faster clearance from normal organs, e.g., the liver, kidney, spleen, and lung, compared to that in tumors. Both imaging and PDT efficacy of the conjugates were performed in BALB/c mice bearing Colon26 tumors. Compared to the others, the short linker conjugate showed poor tumor fluorescent properties and as a corollary does not exhibit the dual functionality of the photosensitizer-fluorophore conjugate. For this reason, it was not evaluated for in vivo PDT efficacy. However, in Colon26 tumor cells (in vitro), the short linker was highly effective. Among the conjugates with variable linkers, the rate of energy transfer from the purpurinimide moiety to the cyanine moiety increased with deceasing linker length, as examined by femtosecond laser flash photolysis measurements. No electron transfer from the purpurinimide moiety to the singlet excited state of the cyanine moiety or from the singlet excited state of the cyanine moiety to the purpurinimide moiety occurred as indicated by a comparison of transient absorption spectra with spectra of the one-electron oxidized and one-electron reduced species of the conjugate obtained by spectroelectrochemical measurements.

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Synthesis, photophysical and electrochemical properties of pyridine, pyrazine and triazine-based (D-?-)₂A fluorescent dyes.

Publications

Synthesis, photophysical and electrochemical properties of pyridine, pyrazine and triazine-based (D-π-)<sub>2</sub>A fluorescent dyes.

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Dataset Information

Synthesis, photophysical and electrochemical properties of pyridine, pyrazine and triazine-based (D-?-)2A fluorescent dyes.

Publications

Synthesis, photophysical and electrochemical properties of pyridine, pyrazine and triazine-based (D-π-)<sub>2</sub>A fluorescent dyes.

Similar Datasets

OmicsDI is part of the ELIXIR infrastructure

Tweets

Synthesis, photophysical and electrochemical properties of pyridine, pyrazine and triazine-based (D-?-)₂A fluorescent dyes.