Related Experiment Video
Updated: Aug 23, 2026

Monitoring the Effects of Illumination on the Structure of Conjugated Polymer Gels Using Neutron Scattering
Published on: December 21, 2017
The surprising nonlinear optical properties of conjugated polyyne oligomers
Aaron D Slepkov1, Frank A Hegmann, Sara Eisler
1Department of Physics, University of Alberta, Edmonton, Alberta T6G 2J1, Canada.
Abstract:
Polyynes represent a unique class of conjugated organic compounds. The third-order nonlinear optical response of polyynes has been extensively modeled theoretically, and it is generally believed that the increase in molecular second hyperpolarizability (gamma) as a function of length for polyynes should be lower than that for polyenes. Experimental evidence to test this prediction, however, has been absent. We have synthesized conjugated polyynes that contain up to 20 consecutive sp-hybridized carbons, and we have determined their nonresonant gamma-values as a function of the number of acetylene repeat units (n). These gamma-values demonstrate a power-law behavior versus n(gamma approximately n(4.28+/-0.13)), with an exponent that is both larger than theoretically predicted for polyynes and substantially higher than that observed for polyenes or polyenynes. Furthermore, no saturation of the linear or nonlinear optical properties is observed.
Related Concept Videos
¹H NMR: Long-Range Coupling
In alkenes, spin information is communicated via σ–π overlap, as seen in allylic (four-bond) and homoallylic (five-bond) couplings. These coupling interactions are stronger when the σ bond is parallel to the alkene π orbitals.
Stability of Conjugated Dienes
A comparison of the enthalpies of hydrogenation of dienes reveals that conjugated dienes release less heat on hydrogenation, rendering them more stable than their nonconjugated analogs.
Photochemical Electrocyclic Reactions: Stereochemistry
Selection Rules: Photochemical Activation
Polymer Classification: Stereospecificity
Polymer Classification: Architecture
Polymers: Molecular Weight Distribution

