Poly(p-diethynylbenzene) Derivatives for Nonlinear Optics

Abstract

A new series of poly(p‐diethynylbenzene) derivatives with trans structure and long‐conjugation side chains were synthesized. These polymers possess good solubility and thermal stability. The maximum absorptions and band gaps depend on the nature and number of the substituents. Third‐order nonlinear optical properties of these polymers were characterized with second‐order hyperpolarizability as large as ≈10–30 esu in the non‐resonant region.

Polymerization of Substituted Acetylenes Carrying Non-Polar and Polar Groups with Transition Metal Acetylide Catalysts

“…[7f] In addition, the branched structure of poly(p-DEB) is further proved by broad and multimodal molecular weight distribution (M -w /M -n as large as 3.8) and small Mark-Houwink constants (a as small as 0.26). [16] Poly[(pphenylethynyl)phenylacetylene] and poly[p-(2-thienylethynyl)phenylacetylene] have a linear p-conjugated polyene chain structure, as confirmed by elemental analysis, FT-IR, 1 H NMR, 13 C NMR and UV spectra, [12] because only terminal but not internal carbon-carbon triple bond can be cleaved.…”

“…Six nickel and palladium acetylide complexes containing phosphine ligands, such as Ni(PPh 3 ) 2 (C3CC 6 H 4 -C3CH) 2 , [8] Ni(PBu 3 ) 2 (C3CC 6 H 4 C3CH) 2 , [8] Pd(PPh 3 ) 2 (C3CC 6 H 4 C3CH) 2 , [9] Pd(PBu 3 ) 2 (C3CC 6 H 4 C3CH) 2 , [10] Pd(PPh 3 ) 2 (C3CCH 2 OH) 2 [7a] and Pd(PBu 3 ) 2 (C3CCH 2 OH) 2 [7d] were prepared from nickel and palladium chloride complexes with phosphine ligands and substituted acetylenes in diethylamine with or without CuI as the catalyst. Monomers, such as p-DEB, [11] propargyl alcohol acetate, [7b] propargyl alcohol benzoate, [7c] p-(phenylethynyl)phenylacetylene [7e] and p-(2-thienylethynyl)phenylacetylene [12] were prepared according to the literature.…”

Electropolymerizable 2,2′-Carboranyldithiophenes. Structure−Property Investigations of the Corresponding Conducting Polymer Films by Electrochemistry, UV−Visible Spectroscopy and Conducting Probe Atomic Force Microscopy

“…Compound 5 was prepared in 71% yield as a yellow powder using Sonogashira coupling according to a literature procedure 34. A mixture of decaborane (2.44 g, 3.0 mmol) and diethyl sulfide (9.0 mL, 37 mmol) in 20 mL of dry toluene was heated at 40 °C for 2 h under argon, and then the temperature was raised to 60 °C for 3 h. Then 5 (1.45 g, 5 mmol) in 20 mL of toluene was added into the mixture by syringe, and the mixture was heated at 80 °C for 2 days under argon.…”

Resonant Third-Order Optical Nonlinearities of Chloroform Solution and Neat Film of Poly(9,9-dioctylfluorenyl-2,7-yleneethynylene)

“…Conjugated polymers have attracted considerable interest because of the ultrafast and large optical nonlinearity attributed to the one dimensionality and delocalization of electrons along the polymer chain. [1][2][3][4][5][6][7][8][9] Future nonlinear optical devices such as logic devices, optical switches, modulators and other all-optical devices are likely to operate at a bandwidth of hundreds of GHz with only a few mW average laser power, thus the ultrafast response and the large third-order optical nonlinearity of conjugated polymers make them attractive candidates for their applications. 8,10) The ease of fabrication and the molecular engineering of their structure are some of the additional advantages of conjugated polymers for use in future optical nonlinear devices.…”