Quarternization of 3-azido-1-propyne oligomers obtained by copper(I)-catalyzed azide–alkyne cycloaddition polymerization

Nakano, Susumu; Hashidzume, Akihito; Sato, Takahiro

doi:10.3762/bjoc.11.116

Cited by 6 publications

(8 citation statements)

References 50 publications

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“…101 A first step consisted in the CuAAC polyaddition of 3-azido-1-propyne generated in-situ from the reaction between propargyl bromide and sodium azide. Indeed, the generation of 3-azido-1-propyne in a separate step prior to CuAAC polyaddition would afford an extremely reactive and potentially explosive organic azide (i.e.…”

Section: Tpils Obtained Via Cuaac Polyadditionmentioning

confidence: 99%

Poly(1,2,3-triazolium)s: a new class of functional polymer electrolytes

2016

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Poly(ionic liquid)s (PILs) are a unique class of polyelectrolytes having properties suited for modern technological applications such as electrochemical devices (batteries, supercapacitors, light-emitting electrochemical cells), ion-gated field effect transistors, electrochromic devices, fuel cells, dye sensitized solar cells, catalysis, or soft robotics. Their structure and properties can be finely tuned by unlimited combinations issued from extended pools of cationic and anionic building blocks. In a constant quest for the development of solid polymer electrolytes with enhanced physical, mechanical and (electro)chemical properties, a new class of PILs based on 1,2,3-triazolium cations has been recently developed. Their preparation takes advantage of the beneficial features of the multiple combinations between the Click chemistry philosophy with macromolecular engineering techniques to afford tunable and highly functional ion conducting materials thus stretching out the actual boundaries of PILs macromolecular design. This feature article summarizes the different strategies developed so far for the synthesis of 1,2,3-triazolium-based PILs (TPILs) since their first introduction in 2013.

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Section: Tpils Obtained Via Cuaac Polyadditionmentioning

confidence: 99%

Poly(1,2,3-triazolium)s: a new class of functional polymer electrolytes

2016

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“…These samples were characterized by SEC and 1 H NMR as can be seen in Figures S1–S3 in the Supporting Information. Our previous work has demonstrated that AP homopolymer is insoluble in all the common solvents examined, including DMF, DMSO, N -methylpyrrolidone (NMP), methanol, acetone, THF, chloroform, and toluene [21,22]. Thus, the solubility of the EG m - b -AP n diblock copolymer samples was examined, and the results are summarized in Table 2.…”

Section: Resultsmentioning

confidence: 99%

“…This observation indicates that protonation makes the oligomers soluble. The AP oligomer was thus quarternized with methyl iodide to obtain an oligomer soluble in polar organic solvents [22]. Since the quarternized oligomer possesses dense quaternized 1,2,3-triazole moieties, it can be expected to be a precursor of polymeric ionic liquid [23,24,25].…”

Section: Introductionmentioning

confidence: 99%

Emission Properties of Diblock Copolymers Composed of Poly(ethylene glycol) and Dense 1,2,3-Triazole Blocks

2019

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This article describes a new block copolymer (EGm-b-APn, where m and n denote the degrees of polymerization) of poly(ethylene glycol) (PEG) and poly(1,4-(1-H-1,2,3-triazolylene)methylene) prepared by copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC) polymerization of 3-azido-1-propyne (AP) in the presence of PEG carrying a propargyl moiety. The EGm-b-APn samples are well soluble in polar organic solvents. Unexpectedly, we observed that solutions of EGm-b-APn in N,N-dimethylformamide emitted fluorescence. We systematically studied absorption and emission properties of the block copolymers. The experimental data have exhibited that APn block is an intrinsic fluorophore. Interestingly, the emission of EGm-b-APn can be easily tuned from ultraviolet to green fluorescence by changing the excitation wavelength. This enables fine-tuning of its optical property without the need of changing the chromophore. Moreover, the block copolymers show a fluorescence response to metal ions (e.g., Cu2+). Our discoveries contribute to the fundamental understanding of the optical properties of dense triazole-based polymer and raise intriguing prospects for fabricating novel emissive triazole-based materials.

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“…Because of the poor solubility, it was not possible to obtain high-molecular-weight polymers from the AP derivatives by CuAAC polymerization. However, it was possible to obtain dense 1,2,3-triazole oligomers or polymers soluble in common solvents by quaternization of the AP oligomer with methyl iodide [ 34 ] or by connecting to poly(ethylene glycol) (PEG) blocks, i.e., the formation of block copolymers [ 35 , 36 ]. The block copolymers of PEG and dense 1,2,3-triazole blocks form aggregates in water, e.g., spherical micelles and vesicles, depending on the ratio of block lengths, and undergo phase separation at higher temperatures because of cooperative dehydration of the PEG block [ 36 ].…”

Section: Introductionmentioning

confidence: 99%

Synthesis of Dense 1,2,3-Triazole Polymers Soluble in Common Organic Solvents

Yamasaki

Kamon

et al. 2021

Polymers

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Aiming at synthesis of dense 1,2,3-triazole polymers soluble in common organic solvents, a new 3-azido-1-propyne derivative, i.e., t-butyl 4-azido-5-hexynoate (tBuAH), was synthesized and polymerized by copper(I)-catalyzed azide–alkyne cycloaddition (CuAAC) and Huisgen cycloaddition (HC). CuAAC polymerization produced poly(tBuAH) composed of 1,4-disubstituted 1,2,3-triazole units (1,4-units), whereas HC polymerization gave poly(tBuAH) composed of 1,4- and 1,5-disubstituted 1,2,3-triazole units (1,4- and 1,5-units). In HC polymerization, the fraction of 1,4-unit (f1,4) decreased with the permittivity of solvent used. Differential scanning calorimetry data indicated that the melting point of poly(tBuAH) increased from 61 to 89 °C with increasing f1,4 from 0.38 to 1.0, indicative of higher crystallinity of poly(tBuAH) composed of 1,4-unit. Preliminary steady-state fluorescence study indicated that all the poly(tBuAH) samples of different f1,4 emitted weak but significant fluorescence in DMF. The maximum of fluorescence band shifted from ca. 350 to ca. 450 nm with varying the excitation wavelength from 300 to 400 nm.

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Quarternization of 3-azido-1-propyne oligomers obtained by copper(I)-catalyzed azide–alkyne cycloaddition polymerization

Cited by 6 publications

References 50 publications

Poly(1,2,3-triazolium)s: a new class of functional polymer electrolytes

Poly(1,2,3-triazolium)s: a new class of functional polymer electrolytes

Emission Properties of Diblock Copolymers Composed of Poly(ethylene glycol) and Dense 1,2,3-Triazole Blocks

Synthesis of Dense 1,2,3-Triazole Polymers Soluble in Common Organic Solvents

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