Surface Organization, Light-Driven Surface Changes, and Stability of Semifluorinated Azobenzen Polymers
A series of polymers with 4-perfluoroalkyl-modified azobenzene side groups was investigated for its light-induced changes in surface properties. The ultraviolet (UV) light activated trans to cis isomerization of the azobenzene group, and the influence of molecular order and orientation on this process were studied using near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and water contact angle measurements. Light-induced molecular reorganization in the near-surface region was studied by NEXAFS using in situ UV irradiation of polymer thin films. Differential scanning calorimetry and wide-angle X-ray scattering studies showed that sufficiently long fluoroalkyl groups formed well-ordered smectic mesophases in the bulk, as well as on the surface, which was evidenced by NEXAFS. The disruption of mesogen packing by photoisomerization was found to be influenced by the fluoroalkyl segment length. Surfaces with perfluorohexyl and perfluorooctyl groups that showed high orientational order were also highly resistant to light-induced changes. In such cases, the trans-cis isomerization resulted in greater lowering of the azobenzene phenyl ring order parameters than the perfluoroalkyl order parameters. UV exposure caused reorientation of the phenyl rings of the azobenzene group, but the terminal perfluoroalkyl segments remained more or less ordered.
- Research Organization:
- Brookhaven National Lab. (BNL), Upton, NY (United States). National Synchrotron Light Source
- Sponsoring Organization:
- Doe - Office Of Science
- DOE Contract Number:
- DE-AC02-98CH10886
- OSTI ID:
- 930362
- Report Number(s):
- BNL-81081-2008-JA; LANGD5; TRN: US200904%%526
- Journal Information:
- Langmuir, Vol. 23; ISSN 0743-7463
- Country of Publication:
- United States
- Language:
- English
Similar Records
Nonadiabatic ab initio molecular dynamics of photoisomerization in bridged azobenzene
Ab initio molecular dynamics simulation of photoisomerization in azobenzene in the n{pi}* state