Tunable SiN Hybrid Conjugated Materials

Folster, Carlton P.; Nguyen, Phi Nga; Siegler, Maxime A.; Klausen, Rebekka S.

doi:10.1021/acs.organomet.9b00254

Cited by 6 publications

(10 citation statements)

References 50 publications

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“…Thiophenol, 4-bromothiophenol, p-thiocresol, and benzene-d 6 were all purchased from commercial sources. 1 H NMR, 13 C { 1 H} NMR, and 29 Si { 1 H} NMR spectra were recorded on either a Bruker Advance 300, 400, or III HD 400 MHz spectrometer, and chemical shifts are reported in parts per million (ppm). Spectra were recorded in benzene-d 6 or chloroform-d 1 with the residual solvent peak as the internal standard ( 1 H NMR: C 6 H 6 δ = 7.16, CHCl 3 δ = 7.26; 13 C NMR: C 6 H 6 δ 128.06, CHCl 3 δ = 77.16).…”

Section: ■ Conclusionmentioning

confidence: 99%

“…Since the discovery in the 1960s that permethylcyclosilanes exhibit longer-wavelength absorption spectra than cycloalkanes and form stable radical anions, interest in the synthesis of increasingly complex cyclosilanes has only grown . Prismatic solids , and polycyclic silanes have shed light on the impact of strain and curvature on σ-conjugation, while we have investigated the synthesis of stereochemically defined cyclosilanes. − An interest in the influence of heteroatomic substitution on optoelectronic properties has inspired work on boron- − and nitrogen-containing cyclosilanes. , Herein, we report the synthesis of cyclosilane thioethers via chemoselective dehydrocoupling of partially hydrogenated cyclosilanes and arylthiols and examine the effect of structural isomerism on conjugation. Density functional theory (DFT) calculations were used to elucidate potential mechanisms underlying experimental observations.…”

Section: Introductionmentioning

confidence: 99%

“…7−9 An interest in the influence of heteroatomic substitution on optoelectronic properties has inspired work on boron- 10−12 and nitrogen-containing cyclosilanes. 13,14 Herein, we report the synthesis of cyclosilane thioethers via chemoselective dehydrocoupling of partially hydrogenated cyclosilanes and arylthiols and examine the effect of structural isomerism on conjugation. Density functional theory (DFT) calculations were used to elucidate potential mechanisms underlying experimental observations.…”

Section: ■ Introductionmentioning

confidence: 99%

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Conjugation in Isomeric Cyclosilane Thioethers

et al. 2022

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Conjugation in thioether-functionalized cyclosilanes depends on both conformation and connectivity. Borane-catalyzed dehydrocoupling of thiophenols with partially hydrogenated cyclosilanes proceeded with high chemoselectivity for Si−H bonds in the presence of Si−Si bonds. Isomeric 1,3and 1,4-functionalized cyclosilanes afforded isomeric cyclosilane thioethers that also differed in preference for chair or twist-boat conformations as demonstrated by both X-ray crystal structures and density functional theory (DFT) calculations. The confounding effects of different conformations and connectivity could be distinguished with time-dependent DFT (TD-DFT) calculations and validated with experimentally obtained UV−vis spectra.

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Section: ■ Conclusionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Conjugation in Isomeric Cyclosilane Thioethers

et al. 2022

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“…Other studies have shown that permethylated oligosilanes can be induced with light to donate electrons to the electron acceptor tetracyanoethylene (TCNE), suggesting that σ–π conjugated hybrid materials might be expected to exhibit photoinduced intramolecular charge-transfer. These discoveries prompted the design of new organosilane materials with silane-bridged donor–acceptor units as a common architecture − and the interrogation of their photoinduced charge-transfer and nonlinear optical behaviors.…”

Section: Introductionmentioning

confidence: 99%

Intramolecular Photoinduced Charge Transfer and Recombination Dynamics in Vinylarene Terminated Organosilanes

et al. 2021

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We report on charge-transfer dynamics of newly designed acceptor−donor− acceptor organosilanes, with a specific focus on how donor−acceptor combination and local chemical environment can be used to control the lifetime for intramolecular charge-separation between silane electron donors and organic acceptors. In this work linear oligosilanes were capped with arene-vinyl end groups of variable electron-accepting strength: weak (diester vinyl), intermediate (ester,cyano vinyl), and strong (dicyanovinyl). Ultrafast transient absorption spectroscopy was used to characterize their structure-dependent charge-transfer and recombination behaviors. All structures exhibit similar photoinduced ultrafast spectral dynamics that we ascribe to relaxation of the nascent charge-separated excited state followed by a return to the ground state via charge recombination. We find that relaxation of the nascent "hot" chargeseparated excited state scales with the strength of dipole−dipole interactions between solvent molecules and the polar arene-vinyl acceptor. Furthermore, electron-accepting strength governs whether electronic coupling dictates charge recombination rate: weak acceptors produce charge-separated states that exhibit relatively large electronic coupling for back-electron transfer (approaching the adiabatic limit) that result in fast recombination, whereas the strong and moderate-strength acceptors support more stable charge-separated states with weaker coupling and longer lifetimes. We find that recombination rates increase substantially for structures with weak and moderate-strength acceptors in cyclohexane (i.e., negligible solvent reorganization energy), which we attribute to an increased electronic coupling in a nonpolar solvent environment where charge pairs are weakly screened. In contrast, for structures with strong electron acceptors, the very low reorganization energy of cyclohexane places back-electron transfer even further into the Marcus inverted regime, with a resultant increase in charge-separation lifetime. Together these results provide critical insights on how to tune photoinduced charge-transfer behavior in organic−inorganic hybrids that have potential material applications in molecular electronics and optoelectronics.

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“…[15] Towards the goal of uncovering new nanostructured materials that combine these compelling properties with the processability and tunability of organic conjugated polymers, we reported the synthesis of organosilicon polymer mimics of the crystalline silicon lattice such as polycyclosilane poly(1,4Si 6 ) (Scheme 1a). [16] Key to this work is the synthesis of multifunctional cyclosilanes [17,18] amenable to dehydrocoupling [19][20][21][22][23] or reductive polymerization. [24] The rational design and synthesis of new building blocks could further expand the structural and functional diversity of polycyclosilanes and other nanostructured silanes.…”

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Isolation of a Cyclopentasilane from Magnesium Reduction of a Linear Hexasilane

et al. 2021

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The reductive cyclization of two linear hexasilanes is contrasted, where a methylated precursor yielded a cyclohexasilane while the tert‐butyl‐functionalized analog unexpectedly yielded a cyclopentasilane. A comprehensive analysis using X‐ray diffraction, IR, HR, HRMS, and multinuclear (1H, 13C and 29Si) 1D and 2D NMR spectroscopy identified the 1,2‐dihydrodisilane tBuPhHSi‐SiHPhtBu as an additional product, which was interpreted as supportive of a mechanism involving silylene elimination. The results of this study may prove informative about substituent effects in the practice of complex organosilicon molecular synthesis.

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Tunable SiN Hybrid Conjugated Materials

Cited by 6 publications

References 50 publications

Conjugation in Isomeric Cyclosilane Thioethers

Conjugation in Isomeric Cyclosilane Thioethers

Intramolecular Photoinduced Charge Transfer and Recombination Dynamics in Vinylarene Terminated Organosilanes

Isolation of a Cyclopentasilane from Magnesium Reduction of a Linear Hexasilane

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