Polydiacetylenes from Asymmetrically Substituted Diacetylenes Containing Heteroaryl Side Groups for Third-Order Nonlinear Optical Properties

Abstract

Synthesis of a series of asymmetrically substituted diacetylenes containing a thienyl moiety or a quinolyl moiety as one of the side groups directly bound to diacetylene and a urethane group as the other one was carried out. Though some of the prepared diacetylenes could be polymerized in solid state by using UV and γ-radiation, all of them were stable when heat was used as the stimulus. The monomer to polymer conversion for the polymerizable ones was found to be in the range 35−60%. Various spectroscopic techniques, such as FTIR, solid state 13C NMR and visible absorption spectroscopies, and powder X-ray diffraction were used to elucidate the structures of the polydiacetylenes. One of the polymers containing quinolyl moiety as directly bound side group showed unusually long and sharp absorption maximum indicating long and uniform conjugated chains. Third-order nonlinear optical susceptibility, χ(3), of two of the polymers were measured using Maker's fringe technique. The largest value for χ(3) in the resonant region for polymer backbone direction in single crystalline form was estimated to be on the order of 10-11 esu.

A Combinatorial Approach for Colorimetric Differentiation of Organic Solvents Based on Conjugated Polymer‐Embedded Electrospun Fibers

“…[1] Among the conjugated polymers reported to date, PDAs are unique in several regards. [2][3][4][5][6][7][8][9][10][11][12][13][14][15][16] First, these polymers can be prepared from supramolecularly assembled crystalline or semi-crystalline states of diacetylene (DA) monomers. Conventional solution-based chemical approaches typically employed for the preparation of conjugated polymers do not yield PDAs efficiently.…”

High Molecular Orientation in Mono- and Trilayer Polydiacetylene Films Imaged by Atomic Force Microscopy

“…These two-dimensional polydiacetylene films, where the conjugation runs parallel to the film surface, have been prepared as Langmuir monolayer (2), Langmuir-Blodgett (LB) multilayer films (3), bilayer systems (4), and self-assembled monolayer (SAM) (5). Numerous applications for these films have been explored, including biomimetic surfaces for protein studies (6), biosensors (7), NLO materials (8), and biomineralization templates (9).…”

Solid-state polymerization of conjugated hexayne derivatives with different end groups

“…In this connection, we have synthesized ladder-type PDAs, in which two polymer backbones were introduced in a repeating unit. 11,12 In addition, several PDAs with p-conjugated substituents, such as aromatic rings and C-C multiple bonds, directly bound to the polymer backbone [13][14][15][16][17][18][19][20][21][22] have been synthesized to obtain PDAs with absorption maxima at longer wavelengths, resulting in larger w (3) -values. In particular, oligoyne derivatives with five or more conjugated acetylenes yielded ladder polymers with p-conjugation between two PDA backbones, as shown in Figure 1.…”