Effect of hydrogen-bond strength on photoresponsive properties of polymer-azobenzene complexes

• Published in: Canadian journal of chemistry Vol. 98; no. 9; pp. 531 - 538
• Main Authors: Vapaavuori, Jaana, Koskela, Jenni E, Wang, Xiaoxiao, Ras, Robin H.A, Priimagi, Arri, Bazuin, C. Geraldine, Pellerin, Christian
• Format: Journal Article
• Language: English
• Published: 1840 Woodward Drive, Suite 1, Ottawa, ON K2C 0P7 NRC Research Press 01-09-2020; Canadian Science Publishing NRC Research Press
• Subjects: Analysis; Azo compounds; Azo polymers; azo-containing materials; Bonding strength; Carboxylic acids; Chromophores; Complexation; complexes supramoléculaires; composés azoïques; Crystallization; Diffraction efficiency; Diffraction patterns; Dimerization; Hydrogen; Hydrogen bonding; Hydroxides; Phase separation; photo-orientation; Polymers; Polyvinyl pyridine; réseaux de surface; supramolecular complexes; surface relief gratings; Canada
• ISSN: 0008-4042; 1480-3291
• DOI: 10.1139/cjc-2020-0048

Supramolecular complexation between photoresponsive azobenzene chromophores and a photopassive polymer host offers synthetic and design advantages compared with conventional covalent azo-containing polymers. In this context, it is important to understand the impact of the strength of the supramolecular interaction on the optical response. Herein, we study the effect of hydrogen-bonding strength between a photopassive polymer host [poly(4-vinylpyridine), or P4VP] and three azobenzene analogues capable of forming weaker (hydroxyl), stronger (carboxylic acid), or no H-bonding with P4VP. The hydroxyl-functionalized azo forms complete H-bonding complexation up to equimolar ratio with VP, whereas the COOH-functionalized azo reaches only up to 30% H-bond complexation due to competing acid dimerization that leads to partial phase separation and azo crystallization. We show that the stronger azo-polymer H-bonding nevertheless provides higher photoinduced orientation and better performance during optical surface patterning, in terms of grating depth and diffraction efficiency, when phase separation is either avoided altogether or is limited by using relatively low azo contents. These results demonstrate the importance of the H-bonding strength on the photoresponse of azopolymer complexes, as well as the need to consider the interplay between different intermolecular interactions that can affect complexation.