214920-46-4Relevant articles and documents
Discotic liquid crystals of transition metal complexes 58: Novel phthalocyanine-based mesogenic monomers and polymers exhibiting spontaneous homeotropic alignment and helical tetragonal columnar structure
Suzuki-Ichihara, Ayumi,Sugibayashi-Kajita, Makiko,Ariyoshi, Masahiro,Yasutake, Mikio,Ohta, Kazuchika
, p. 800 - 817 (2021/05/27)
Two synthetizations of a novel series of phthalocyanine-based discotic liquid crystals substituted by a polymerizable group, acryloyl group or a norbornene group: 2-(12-acryloyloxydodecyloxy)-3-methoxy-9,10,16,17,23,24-hexakis (3,4-dialkoxyphenoxy)phthalocyaninato copper(II) [abbreviated as (n,12)PcCu(OCH3)(Acryloyl) (7: e (n = 10), f (n = 12), g (n = 14))] and 2-(12-norborn-2-ene carbonyloxydodecyloxy)-3-methoxy-9,10,16,17,23,24-hexakis(3,4-dialkoxyphenoxy)-phthalocyaninato copper(II): [abbreviated as (n, 12)PcCu(OCH3)(Norb) (9e, f, g)]. Their liquid crystalline properties and homeotropic alignment were investigated using a polarizing microscope, a differential scanning calorimetry (DSC), and a temperature-variable X-ray diffractometer. As a result, each of the derivatives gave a Coltet mesophase in the higher temperature region, displaying perfect homeotropic alignment between the two glass plates. In order to obtain the thin film while keeping their homeotropic alignment at room temperature, attempts to polymerize the monomers, 7 and 9, in the Coltet phase showed homeotropic alignment. The polymerization of the acryloyl-substituted monomers (7) was not successful in any of the methods, whereas the polymerization of norbornene-substituted monomers (9) was quite successful by ring-opening metathesis polymerization with a Grubbs catalyst to obtain the novel polymers, poly-(n, 12)PcCu(OCH3)(Norb) (10e, f, g). Each of the polymers (10) were found to show a perfect homeotropic alignment from room temperature to ca. 200°C of the decomposition temperature. Moreover, it was also revealed from temperature-variable small-angle X-ray diffraction studies that each of the polymers 10 showed a helical Coltet (helical tetragonal columnar) structure. The helical Coltet phase structure may be able for use in organic electroluminescent devices and solar cells in the future.
Ion Conducting ROMP Monomers Based on (Oxa)norbornenes with Pendant Imidazolium Salts Connected via Oligo(oxyethylene) Units and with Oligo(ethyleneoxy) Terminal Moieties
Price, Terry L.,Choi, U Hyeok,Schoonover, Daniel V.,Arunachalam, Murugan,Xie, Renxuan,Lyle, Steven,Colby, Ralph H.,Gibson, Harry W.
, p. 1371 - 1388 (2019/02/19)
A matrix of 22 two-armed norbornene-based imidazolium TFSI monomers (8) was synthesized to determine the optimal structure in terms of single ion conductivity. For the chain tethering the imidazolium ring to the norbornene ring three or four oxyethylene units are optimal. A terminal group of two ethyleneoxy units was optimal. NMR studies indicated that both the tether oxyethylene units and the terminal ethyleneoxy units interact with the imidazolium cation via hydrogen bonding. 8r (X = 4, Y = 2) exhibited a conductivity of 9.57 × 10-5 S/cm at 25 °C and a Tg of -46 °C. Low Tg values do not correlate with higher conductivity as a result of the H-bonding interactions. Stability toward autopolymerization and reasonable conductivities provide an acceptable platform for ion conducting ROMP polymers. Four one-armed norbornene-based imidazolium TFSI monomers (15) were prepared with tetra(ethyleneoxy) linkers/spacers and variable terminal groups. All of these exhibited low Tgs (10-4 S/cm, the highest being 4.39 × 10-4 S/cm for 15c (Tg = -69 °C), the analogue of 8r, providing hope for outstanding polymers. Three oxanorbornene-based two-armed imidazolium TFSI monomers (18) were prepared with varied linkers and terminal groups. 18b possesses a room temperature conductivity of 1.2 × 10-4 S/cm, again augering well for polymers derived therefrom by ROMP.
Natural Triterpenoid- and Oligo(Ethylene Glycol)-Pendant-Containing Block and Random Copolymers: Aggregation and pH-Controlled Release
Li, Ying,Gao, Yuxia,Wang, Bo,Hao, Jie,Hu, Jun,Ju, Yong
supporting information, p. 2723 - 2729 (2018/09/06)
In this research, a series of random and block amphiphilic copolymers of norbornene derivatives containing biocompatible natural triterpenoid and oligo(ethylene glycol) pendants were synthesized by ring-opening metathesis polymerization. These copolymers were heat and pH responsive, and could self-assemble into core–shell spherical micelles in aqueous solution. Their hydrodynamic diameters corresponded to pH values and monomer sequences. By evaluating the loading and release capacity of hydrophobic molecules, it was found that 1) the higher the content of the hydrophobic triterpenoid, the higher the loading capacity; 2) the release speed could be trigged by the pH because of the deprotonation of the carboxyl groups on the triterpenoid. Additionally, the copolymers exhibited low cytotoxicity toward L929 cells, which makes them potential nanocarrier candidates for controlled drug delivery.
