Jump to main content
Jump to site search
Access to RSC content Close the message box

Continue to access RSC content when you are not at your institution. Follow our step-by-step guide.


Issue 6, 2015
Previous Article Next Article

Internal organization of macromonomers and dendronized polymers based on thiophene dendrons

Author affiliations

Abstract

The internal organization of macromonomers (MGs) consisting of all-thiophene dendrons of generation g = 2 and 3 attached to a phenyl core, as well as of the dendronized polymers resulting from polymerization of these macromonomers (PG2 and PG3, respectively), has been investigated using theoretical methods. The conformational preferences of the MGs, determined using density functional theory calculations, are characterized by the relative orientation between dendrons and core. We find that the strain of the MGs increases with the generation number and is alleviated by small conformational re-arrangements of the peripheral thiophene rings. The conformations obtained for the MGs have subsequently been used to construct models for the dendronized polymers. Classical molecular dynamics simulations have evidenced that the interpenetration of dendrons belonging to different repeat units is very small for PG2. In contrast, the degree of interpenetration is found to be very high for PG3, which also shows a significant degree of backfolding (i.e. occurrence of peripheral methyl groups approaching the backbone). Consequently, PG2 behaves as a conventional linear flexible polymer bearing bulk pendant groups, whereas PG3 is better characterized as a semirigid homogeneous cylinder. The two polymers are stabilized by π–π stacking interactions, even though these are significantly more abundant for PG3 than for PG2; the average numbers of interactions per repeat unit are 3.0 and 8.8 for PG2 and PG3, respectively. While in these interactions the thiophene rings can adopt either parallel (sandwich) or perpendicular (T-shaped) dispositions, the former scenario turns out to be the most abundant.

Graphical abstract: Internal organization of macromonomers and dendronized polymers based on thiophene dendrons

Back to tab navigation

Article information


Submitted
13 Nov 2014
Accepted
11 Dec 2014
First published
11 Dec 2014

Soft Matter, 2015,11, 1116-1126
Article type
Paper
Author version available

Internal organization of macromonomers and dendronized polymers based on thiophene dendrons

E. Córdova-Mateo, O. Bertran, A. D. Schlüter, M. Kröger and C. Alemán, Soft Matter, 2015, 11, 1116
DOI: 10.1039/C4SM02523G

Social activity

Search articles by author

Spotlight

Advertisements