Unusual Reactivity of Group 14 Hydrides toward Organic Halides: Synthetic Studies and Application to Functional Materials

Shimada, Masaki; Yamanoi, Yoshinori; Nishihara, Hiroshi

doi:10.5059/yukigoseikyokaishi.74.1098

Cited by 29 publications

(12 citation statements)

References 85 publications

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“…The absorption band of 5 , which has a bibenzothiadiazole core, exhibited a bathochromic shift relative to 1 – 4 . The effects of the acceptor cores on the shapes of the absorption spectra appeared to be stronger than that of the donor terminal groups, consistent with other disilane-linked molecules previously reported by our group [15,16,17,18,19].…”

Section: Resultssupporting

confidence: 91%

Effects of Substituents on the Blue Luminescence of Disilane-Linked Donor‒Acceptor‒Donor Triads

et al. 2019

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A series of disilane-linked donor‒acceptor‒donor triads (D‒Si‒Si‒A‒Si‒Si‒D) was synthesized to investigate the effects of substituents on the photophysical properties. The triads were prepared by metal-catalyzed diiodosilylation of aryl iodides using a Pd(P(t-Bu)3)2/(i-Pr)2EtN/toluene system that we previously developed. Optical measurements, X-ray diffraction analysis, and density functional theory calculations revealed relationships between the photophysical properties and molecular structures of these triads in solution and in the solid state. The compounds emitted blue to green fluorescence in CH2Cl2 solution and in the solid state. Notably, compound 2 showed fluorescence with an absolute quantum yield of 0.17 in the solid state but showed no fluorescence in CH2Cl2. Our findings confirmed that the substituent adjacent to the disilane moiety affects the conformations and emission efficiencies of compounds in solution and in the solid state.

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Section: Resultssupporting

confidence: 91%

Effects of Substituents on the Blue Luminescence of Disilane-Linked Donor‒Acceptor‒Donor Triads

et al. 2019

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“…1) was prepared according to our previous literature. 36 All solvents used for crystallization were purchased from commercial sources. Solution-state 13 C NMR measurement of 1 was conducted on a JEOL ECX400 spectrometer in CDCl 3 .…”

Section: Introductionmentioning

confidence: 99%

Selective Formation and SHG Intensity of Noncentrosymmetric and Centrosymmetric 1,1,2,2-Tetramethyl-1-(4-(N,N-dimethylamino)phenyl)-2-(2′-cyanophenyl)disilane Crystals under External Stimuli

et al. 2020

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In this paper, selective formation of noncentrosymmetric (Cc; α-crystal) and centrosymmetric (P2 1 /c; 1) was reported and both crystals were characterized by single-crystal X-ray diffraction (XRD) analysis, indicating multiple CH−π interactions created the crystal packing. The second harmonic generation (SHG) activity was attributed to the crystal packing and the orientation of dipole moment. Noncentrosymmetric crystal packing in a parallel manner exhibited SHG activity (intensity: 2.1 times vs urea). On the contrary, centrosymmetric structure in an antiparallel form showed no SHG activity (intensity: 0.0 times vs urea). As the calculated crystal energies of two polymorphs were very close to each other, the regulation of αand β-crystals is succeeded through supercooled liquid-to-crystal and crystal-to-crystal phase transitions, controlling the SHG activity. Powder XRD and solid-state 13 C NMR spectroscopy were applied for the qualitative analysis of αor β-polymorphs.

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“…Thes ynthetic procedure is reported in the experimental section. Pd-catalyzed arylation of monohydrodisilane precursors with aryl iodides,d eveloped by our group over the past decade, [14] afforded pure products after purification by column chromatography on silica gel and then aGPC column. Compound 1 was isolated in 32 %yield as astable crystalline solid (from n-pentane, n-hexane,o ra cetonitrile) or as table amorphous solid (from dichloromethane or chloroform) under an ambient atmosphere.T he molecular structure was characterized by 1 H-and 13 C-NMR spectroscopies,h ighresolution mass spectrometry (Figures S19-S22 and S24 in the supporting information), and single-crystal X-ray diffraction analysis (vide infra).…”

Section: Synthesismentioning

confidence: 99%

Luminescent Behavior Elucidation of a Disilane‐Bridged D–A–D Triad Composed of Phenothiazine and Thienopyrazine

et al. 2021

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A s-p extended aryldisilane,c omprising at hienopyrazine group as an acceptor fragment and phenothiazine groups as the donor moiety,h as been prepared through the introduction of two Si À Si bridges (compound 1). X-ray diffraction analysis determined the crystal structure of 1,a nd experimental and theoretical approaches investigated its optical properties.S olvatochromic studies revealed the dual emission of 1 in all solvents tested. Compound 1 also exhibited fluorescence in the solid state upon excitation with ahand-held UV lamp,a sw ell as mechanochromic luminescent properties. The packing mode in the crystal structure,v ariation of phenothiazine conformation, morphological changes between crystalline and amorphous phases are the major factors showing reversible fluorescence under external stimuli. A theoretical conformer study found that 1 exists in distinct conformational groups differing in Gibbs free energy by less than 3kcal mol À1 .T he conformer in the crystalline state of 1 can promote the complete separation of the HOMO and LUMO between the phenothiazine donor and the thienopyrazine acceptor,l inked by the disilane linker.H OMO-LUMO energy transition in the crystalline state is forbidden due to the lacko ff rontier orbital overlap.C rystalline state emission showed LUMO ! HOMOÀ1transition (locally excited (LE) state). In the amorphous state,t he partial presence of quasiaxial conformers allows intramolecular charge-transfer type emission via energy transfer from dominant quasi-equatorial conformers.T he strategy proposed in this work provides important guidance for developing stimuli-responsive materials with controlled excited states.

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Unusual Reactivity of Group 14 Hydrides toward Organic Halides: Synthetic Studies and Application to Functional Materials

Cited by 29 publications

References 85 publications

Effects of Substituents on the Blue Luminescence of Disilane-Linked Donor‒Acceptor‒Donor Triads

Effects of Substituents on the Blue Luminescence of Disilane-Linked Donor‒Acceptor‒Donor Triads

Selective Formation and SHG Intensity of Noncentrosymmetric and Centrosymmetric 1,1,2,2-Tetramethyl-1-(4-(N,N-dimethylamino)phenyl)-2-(2′-cyanophenyl)disilane Crystals under External Stimuli

Luminescent Behavior Elucidation of a Disilane‐Bridged D–A–D Triad Composed of Phenothiazine and Thienopyrazine

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