Tuning of fluorescence efficiency via local modification of the crystal structure by benzyl groups in polymorphs of a pyrazine dye

Akune, Yoko; Hirosawa, Risa; Endo, Natsuko; Hatano, Sayumi; Hosokai, Takuya; Sato, Hiroyasu; Matsumoto, Shinya

doi:10.1039/c7ce00164a

“…The photophysical properties of crystals of the PDs were also determined. The absorption spectra of PD-H, PD-OCH3, and PD-CF3 crystals, obtained using a waveguide technique, [56][57][58] contain maxima at 352, 422, and 355 nm, respectively, that are similar to those of corresponding CH2Cl2 solutions. The FL spectra of PD-H, PD-OCH3, and PD-CF3 crystals contain maximum at 487, 531, and 467 nm, respectively, which are also close to those of CH2Cl2 solutions.…”

Section: Resultsmentioning

confidence: 85%

Diphenyldihydropentalenediones: Potential Singlet Fission Materials with High Triplet Energy Levels

Nagaoka

¹

,

Matsui²,

Fuki

³

et al. 2022

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0

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2,2,5,5-Tetramethyl-3,6-diphenyl-2,5-dihydropentalene-1,4-dione (PD-H) was developed as a new molecular framework for singlet fission (SF) materials. It was proposed that PD-H and related substances would have high energy level of the triplet-excited state (ET) as a result of the enforcement of molecular planarity through incorporation of ring-fusion constrained diene and avoidance of resonance caused by the presence of amide moieties in the diketopyrrolopyrrole core. Three members of this family (PDs), PD-H, PD-OCH3 (the 4-methoxyphenyl derivative), and PD-CF3 (the 4-(trifluoromethyl)phenyl derivative), were synthesized. The results of photophysical studies revealed that the energy level of singlet-excited state (ES) and ET of PD-H are 2.88 and 1.43 eV, respectively. These values indicate that PD-H has the energy relationship, ES > 2ET, required for it to be a singlet fission material. Moreover, introduction of electron-donating or -withdrawing groups on the benzene rings in PD-H enable fine-tuning of ES and ET while maintaining ES > 2ET. The results of transient absorption spectroscopic studies show that PD-H, PD-OCH3, and PD-CF3 in CH2Cl2 have respective T1 lifetimes of 54, 94, and 108 microsec, which are long enough to utilize its triplet energy as an excitation energy in other optoelectronic systems. These findings suggest that diphenyldihydropentalenediones are potential candidates for SF materials with high ET levels.

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“…The photophysical properties of crystals of the PDs were also determined. The absorption spectra of PD-H, PD-OCH3, and PD-CF3 crystals, obtained using a waveguide technique, [62][63][64] contain maxima at 352, 422, and 355 nm, respectively, that are similar to those of corresponding CH2Cl2 solutions. The FL spectra of PD-H, PD-OCH3, and PD-CF3 crystals contain maximum at 487, 531, and 467 nm, respectively, which are also close to those of CH2Cl2 solutions.…”

Section: Resultsmentioning

confidence: 85%

Diphenyldihydropentalenediones: Potential Singlet Fission Materials with High Triplet Energy Levels

Nagaoka

¹

,

Matsui²,

Fuki

³

et al. 2022

Preprint

0

View full text Add to dashboard Cite

2,2,5,5-Tetramethyl-3,6-diphenyl-2,5-dihydropentalene-1,4-dione (PD-H) was developed as a new molecular framework for singlet fission (SF) materials. It was proposed that PD-H and related substances would have high energy level of the triplet-excited state (ET) as a result of the enforcement of molecular planarity through incorporation of ring-fusion constrained diene and avoidance of resonance caused by the presence of amide moieties in the diketopyrrolopyrrole core. Three members of this family (PDs), PD-H, PD-OCH3 (the 4-methoxyphenyl derivative), and PD-CF3 (the 4-(trifluoromethyl)phenyl derivative), were synthesized. The results of photophysical studies revealed that the energy level of singlet-excited state (ES) and ET of PD-H are 2.88 and 1.43 eV, respectively. These values indicate that PD-H has the energy relationship, ES > 2ET, required for it to be a singlet fission material. Moreover, introduction of electron-donating or -withdrawing groups on the benzene rings in PD-H enable fine-tuning of ES and ET while maintaining ES > 2ET. The results of transient absorption spectroscopic studies show that PD-H, PD-OCH3, and PD-CF3 in CH2Cl2 have respective T1 lifetimes of 54, 94, and 108 microsec, which are long enough to utilize its triplet energy as an excitation energy in other optoelectronic systems. These findings suggest that diphenyldihydropentalenediones are potential candidates for SF materials with high ET levels.

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“…Optical waveguide spectroscopy is known to be a powerful tool for the detection of optical materials because of its good selectivity, high sensitivity, and simultaneous detection of absorption and emission spectra [ 22 ]. It has also been applied to study optical materials and development of an optical sensors [ 23 , 24 , 25 , 26 , 27 ]. In this work, we established an optical measurement system including the synthesis of a fluorescent solvatochromic resin using the Suzuki–Miyaura cross-coupling reaction and the analysis of its specific photophysical properties as the identification of the synthesized compound on the resin surface.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of a Fluorescent Solvatochromic Resin Using Suzuki–Miyaura Cross-Coupling and Its Optical Waveguide Spectra to Measure the Solvent Polarity on the Surface

Otsuka

¹

,

Li

²

,

Takahashi³

et al. 2020

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We have established a novel analytical method for solvent polarity on resin surface by combining the synthesis of fluorescent solvatochromic resin with optical waveguide spectrometry. The fluorescent solvatochromic resin was obtained via Suzuki–Miyaura cross-coupling between 4-iodobenzoic acid immobilized on Wang resin and 5-[4-(N,N-dihexylamino)phenyl]-2-thienylboronic acid N-methyl-iminodiacetic acid (MIDA) ester. The optical waveguide spectrometry studies on the resin showed a strong fluorescent solvatochromism in various organic solvents.

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Tuning of fluorescence efficiency via local modification of the crystal structure by benzyl groups in polymorphs of a pyrazine dye

Cited by 15 publications

References 37 publications

Diphenyldihydropentalenediones: Potential Singlet Fission Materials with High Triplet Energy Levels

Diphenyldihydropentalenediones: Potential Singlet Fission Materials with High Triplet Energy Levels

Diphenyldihydropentalenediones: Potential Singlet Fission Materials with High Triplet Energy Levels

Synthesis of a Fluorescent Solvatochromic Resin Using Suzuki–Miyaura Cross-Coupling and Its Optical Waveguide Spectra to Measure the Solvent Polarity on the Surface

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