Autonomously Substitutable Organosilane Thin Films Based on Dynamic Covalent Diarylbibenzofuranone Units

Yoneyama, Rina; Sato, Tomoya; Imato, Keiichi; Kosuge, Takahiro; Ohishi, Tomoyuki; Higaki, Yasuki; Takahara, Atsushi; Otsuka, Hideyuki

doi:10.1246/cl.150917

Cited by 8 publications

(3 citation statements)

References 35 publications

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“…The precursor compound of Si-DABBF 1, DABBF-bis-(trimethoxysilane), was synthesized by reacting dihydroxy-DABBF (DABBF-diol) with a 2.5-fold excess of 3-isocyanatopropyltrimethoxysilane (IPTMS) in the presence of di-nbutyltin dilaurate (DBTDL) as the catalyst at 35 °C for 2 h (Scheme 1a). 47 The 1 H NMR spectrum of the reaction mixture exhibited a new signal, which was assigned to the −CO−NH− CH 2 − proton, and peak shifts of the methine protons in DABBF-diol and IPTMS (Figure S1 in the Supporting Information). The integral ratio of these peaks was in good agreement with the feed ratio.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…DABBF-containing rigid silica networks, Si-DABBF 1 and 2 , were prepared from the corresponding DABBF-alkoxysilane derivatives by means of a sol–gel method. The precursor compound of Si-DABBF 1 , DABBF-bis(trimethoxysilane), was synthesized by reacting dihydroxy-DABBF (DABBF-diol) with a 2.5-fold excess of 3-isocyanatopropyltrimethoxysilane (IPTMS) in the presence of di- n -butyltin dilaurate (DBTDL) as the catalyst at 35 °C for 2 h (Scheme a) . The 1 H NMR spectrum of the reaction mixture exhibited a new signal, which was assigned to the −CO–N H –CH 2 – proton, and peak shifts of the methine protons in DABBF-diol and IPTMS (Figure S1 in the Supporting Information).…”

Section: Resultsmentioning

confidence: 99%

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Polymer–Inorganic Composites with Dynamic Covalent Mechanochromophore

et al. 2016

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Polymer–inorganic composites with diarylbibenzofuranone (DABBF) moieties, dynamic covalent mechanochromophores, were prepared, and their mechanochromic behavior was systematically investigated. The central C–C bonds in DABBF moieties can be cleaved by mechanical force to form the corresponding stable blue radicals, which can be quantitatively evaluated by electron paramagnetic resonance (EPR) spectroscopy. One controversial issue but attractive property in the DABBF system is the equilibrium between the activated and deactivated states. Although the deactivation process decreases the sensitivity of some equilibrium mechanophores, the equilibrium has rarely been considered when establishing molecular and/or material design of these systems. Herein, a rational macromolecular design to suppress the deactivation of activated dynamic mechanophores and improve sensitivity by limiting their molecular motion is proposed. Polymer–inorganic composite materials with rigid networks prepared from DABBF alkoxysilane derivatives exhibited significant activation of the incorporated DABBF linkages by grinding, with sensitivities more than 50 times as high as that of DABBF monomers. The increased sensitivity is due to the effective transmission of mechanical force to the DABBF moieties in the network structures and suppression of the recombination of the generated radicals by the rigid frameworks. Furthermore, when the rigid frameworks were incorporated into elastomers as inorganic hard domains, the DABBF mechanophores at the interface between the organic and inorganic domains were preferentially activated by elongation.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Polymer–Inorganic Composites with Dynamic Covalent Mechanochromophore

et al. 2016

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“…Imato et al achieved a unique set of conditions. Using as cross‐linker diarylbibenzofuranone (DABBF), the dimer of arylbenzofuranone (ABF, analog to widely used commercial product HP‐136), the polymer gel synthesized was able to undergo self‐healing under mild conditions at room temperature, due to the dynamic covalent bond in its structure.…”

Section: Introductionmentioning

confidence: 99%

Dynamic covalent bond from first principles: Diarylbibenzofuranone structural, electronic, and oxidation studies

2017

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A structure that can self-heal under standard conditions is a challenge faced nowadays and is one of the most promising areas in smart materials science. This can be achieved by dynamic bonds, of which diarylbibenzofuranone (DABBF) dynamic covalent bond is an appealing solution. In this report, we studied the DABBF bond formation against arylbenzofuranone (ABF) and O reaction (autoxidation). Our results show that the barrierless DABBF bond formation is preferred over autoxidation due to the charge transfer process that results in the weakly bonded superoxide. We calculated the electronic and structural properties using total energy density functional theory. © 2017 Wiley Periodicals, Inc.

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Lewis Base Catalyzed Selective Chlorination of Monosilanes

Sturm

Schweizer

Meyer

et al. 2018

Chemistry A European J

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A preparatively facile, highly selective synthesis of bifunctional monosilanes R SiHCl, RSiHCl and RSiH Cl is reported. By chlorination of R SiH and RSiH with concentrated HCl/ether solutions, the stepwise introduction of Si-Cl bonds is readily controlled by temperature and reaction time for a broad range of substrates. In a combined experimental and computational study, we establish a new mode of Si-H bond activation assisted by Lewis bases such as ethers, amines, phosphines, and chloride ions. Elucidation of the underlying reaction mechanisms shows that alcohol assistance through hydrogen-bond networks is equally efficient and selective. Remarkably, formation of alkoxysilanes or siloxanes is not observed under moderate reaction conditions.

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Autonomously Substitutable Organosilane Thin Films Based on Dynamic Covalent Diarylbibenzofuranone Units

Cited by 8 publications

References 35 publications

Polymer–Inorganic Composites with Dynamic Covalent Mechanochromophore

Polymer–Inorganic Composites with Dynamic Covalent Mechanochromophore

Dynamic covalent bond from first principles: Diarylbibenzofuranone structural, electronic, and oxidation studies

Lewis Base Catalyzed Selective Chlorination of Monosilanes

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