Synthesis of poly(phenylacetylene)-based polydendrons consisting of a phenyleneethynylene repeating unit, and oxygen/nitrogen permeation behavior of their membranes

Phenyleneethynylene Macrocycle‐Fused Phenylacetylene Monomers: Synthesis and Polymerization

“…The rhodium catalyst has been reported to be effective for the polymerization of the phenyleneethynylene monodendrons only at the terminal acetylene group of the focal point. [3,7,14] The macrocycle monomers were also polymerized with selective reaction of the terminal acetylene group. For example, in IR and 1 H NMR spectra of poly(6PMDS3), the peaks assignable to the terminal acetylene group of 6PMDS3 -that is, 3 312 cm À1 (the stretching vibration of the C-H bond) in the IR spectrum and d ¼ 3.13 (s, 1H, C-H) in the 1 H NMR spectrumcompletely disappeared.…”

“…[1] On the other hand, poly(phenylacetylene)s -the monomers of which are the same as the repeating units of phenyleneethynylene macrocycleshave attracted attention as one of the interesting functional polymers with magnetic properties, and because of their gas-or enantio-selective permeability membrane properties, and so on. [2][3][4][5][6][7][8][9][10][11][12][13][14][15] The rhodium catalyst can selectively polymerize monosubstituted acetylenes to yield the corresponding polyacetylenes with high degrees of polymerization and stereoregularities, that is, cis-transoidal and helical structures, [16][17][18][19][20][21][22][23][24][25][26][27] while Mo and W catalysts polymerize not only mono-but also disubstituted acetylenes. [28] We previously reported that we succeeded in the polymerization of phenylacetylene monomers with very bulky dendritic side-chains constructed of the phenyleneethynylene repeating units to yield the corresponding poly(phenylacetylene)s with extraordinarily high degrees of polymerization.…”

“…[28] We previously reported that we succeeded in the polymerization of phenylacetylene monomers with very bulky dendritic side-chains constructed of the phenyleneethynylene repeating units to yield the corresponding poly(phenylacetylene)s with extraordinarily high degrees of polymerization. [3,7,14] In this paper, we report the synthesis of monosubstituted acetylenes containing various phenyleneethynylene macrocycles with trimethylsilyl-(TMS) and pentamethyldisiloxanyl-(PMDS) peripheral groups, which are flexible, to afford adequate solvent solubility (see Scheme 1), and the polymerization of these novel monomers with the Phenyleneethynylene macrocycle-substituted acetylenes were synthesized by repetition of the Sonogashira coupling reaction, and the elimination reaction of the terminal acetylene protecting group. The monomers were polymerized with a rhodium catalyst, [Rh(nbd)Cl] 2 , at the terminal acetylene unit, and the polymerization mixtures were purified by precipitating into methanol to yield the corresponding poly(phenylacetylene) derivatives as yellow-red powders, which had a high degree of polymerization (DP % 500) in spite of their steric bulkiness.…”

Polymerization of Phenylacetylene-Based Monodendrons with Alkoxy Peripheral Groups and Oxygen/Nitrogen Permeation Behavior of Their Membranes

“…We have previously synthesized monodendron monomers consisting of m-linked phenyleneethynylene repeating unit with trimethylsilyl peripheral groups and oligo(dimethylsiloxane) chains and obtained the corresponding polydendrons by polymerization of the monomers using a rhodium (Rh) catalyst [5,6]. The polydendrons were mechanically stable and excellent for preparing selfsupporting membranes.…”

Phenylacetylene Dendrimers Containing a Fluorene Core: Synthesis and Spectroscopic Studies

“…Among these dendrimers, stiff dendritic macromolecules with antennas, such as poly(phenyletylene) dendrimers, 1 were the ideal photon-harvesting systems 2-5 with great energy transfer efficiency and 'shape-persistent' dendrimers [6][7][8][9] which have potential applications in fabricating OLEDs, 10,11 sensors, 12,13 catalysis 14 and membranes. [15][16][17] Compared with dendrimers, linear-chain macromolecules may not have the most ideal architecture in the design of artificial photon-harvesting systems for efficient energy transfer. Firstly, it is difficult to make polymeric systems with an energy gradient so that there can be a vectorial transduction of excitation energy.…”