Metathesis Cyclopolymerization of 1,6-Heptadiyne Derivative toward Triphenylamine-Functionalized Polyacetylene with Excellent Optoelectronic Properties and Nanocylinder Morphology

Abstract

Metathesis cyclopolymerization of 1,6-heptadiyne derivatives is readily utilized to synthesize triphenylamine-functionalized polyacetylenes (TPA-PAs) by a third-generation Grubbs catalyst, which selectively generated TPA-PAs with a five-membered ring and all-trans microstructure. The TPA pendants endowed PAs with good solubility and excellent optoelectronic properties (maximum absorption wavelength of 592−605 nm in CHCl 3 , HOMO level of around −5.04 eV, and energy bandgap of 1.82−1.77 eV). When bis-TPA side group was introduced into the PA backbone, the resultant polymer, poly(M2), displayed desirable oxidative stability (up to 30 days stored in THF) and high fluorescence quantum yield (up to 12.3%) in the family of PA derivatives. In addition, poly(M2) could spontaneously self-assemble into the nanocylinder architecture without requiring any tedious postsynthetic treatments. This is the first report that the rigid and immobile conjugated PA segment assembled into the novel cylindrical nanostructure with the aid of π−π interaction of TPA side group.

Branched 1,2,3-Triazolium-Functionalized Polyacetylene with Enhanced Conductivity

“…Compared to poly[ MDTA ] + [ TFSI ] − with the same [M]/[Cat] ratio of 25, the UV–vis spectrum of poly[ DDTA ] + [ TFSI ] − was redshifted about 5 nm, and the intensity of peak at 591 nm increased apparently, though the M n of poly[ MDTA ] + [ TFSI ] − was higher than that of poly[ DDTA ] + [ TFSI ] − . The bigger substituent of poly[ DDTA ] + [ TFSI ] − made polymer chain more well aligned and increased the efficient conjugate length, and the similar phenomenon was observed in our previous work …”

“…In addition, the peaks at 3281 and 3270 cm −1 ascribed to the stretching band of the C−H in [ MDTA ] + [ TFSI ] − (Figure S6a, Supporting Information) and [ DDTA ] + [ TFSI ] − (Figure S6c, Supporting Information) were disappeared in the IR spectra of poly[ MDTA ] + [ TFSI ] − (Figure S6b, Supporting Information) and poly[ DDTA ] + [ TFSI ] − (Figure S6d, Supporting Information), demonstrating the full reaction of CC, which disclosed the proceeding of polymerization. The laser Raman spectra of monomers [ MDTA ] + [ TFSI ] − and [ DDTA ] + [ TFSI ] − (Figure S7a, Supporting Information) showed a characteristic peak at 2117 cm −1 for the CC vibration, which was disappeared after polymerization; at the same time, both poly[ MDTA ] + [ TFSI ] − and poly[ DDTA ] + [ TFSI ] − in Figure S7b (Supporting Information) showed the new characteristic peaks at 1188 and 1540 cm −1 , which were absence in monomers, and assigned to the CC and CC vibrations in the trans ‐PAs, respectively …”

“…Polyacetylene (PA), a representative of the electronic conductive materials, possesses low intrinsic electronic conductivity, low solubility, and poor processability. The metathesis cyclopolymerization (MCP) of 1,6‐heptadiynes provided an approach for obtaining soluble PA with multiple functionalities, and the selective α‐addition of monomer to active center can produce PA with only five‐membered ring units catalyzed by the third‐generation Grubbs catalyst ( Ru ‐ III ) . Coupling PA to ionic conductor could provide the ionic PA (iPA) with ionic and electronic charge dual transport, which allows use of iPA in electrochemical energy storage device …”

Fabrication of nanostructures through self-assembly of non-ionic amphiphiles for biomedical applications

“…A bunch of literature reports reveals that 2,2-di(prop-2-yn-1-yl)propane-1,3-diol has been successfully used as a component for metathesis cyclopolymerization. [26][27][28][29][30][31][32][33] In contrast, there are only two reports wherein the diol has been utilized to afford low-molecular weight amphiphilic molecules. Das et al initiated the synthesis of thiophene-capped cyclopenta[c]thiophene, further functionalized with carbohydrate using the diol for Concanavalin A (protein isolated from jack bean) recognition.…”

Metathesis cyclopolymerization of substituted 1,6‐heptadiyne and dual conductivity of doped polyacetylene bearing branched triazole pendants

“…The catalyst displayed important role on the regioselective cyclopolymerization of diynes . For MCP of 1,6‐heptadiynes catalyzed by the third‐generation Grubbs catalyst ( Ru ‐ III ), the selective α ‐addition of monomer to active center can produce PAs with only five‐membered rings; the solvents showed significant impact on the polymerization behavior, and usually the weakly coordinating solvent such as tetrahydrofuran (THF) was chosen because it could stabilize the active propagating ruthenium (Ru) carbene during the polymerization. The MCP of ionic monomer conducted in THF mixed with ionic liquid was also performed in a controlled manner .…”