TY - JOUR
T1 - Photoswitchable Flexible and Shape-Persistent Dendrimers
T2 - Comparison of the Interplay between a Photochromic Azobenzene Core and Dendrimer Structure
AU - Liao, Li Xin
AU - Stellacci, Francesco
AU - McGrath, Dominic V.
PY - 2004/2/25
Y1 - 2004/2/25
N2 - Two analogous classes of dendrimers with a single azobenzene moiety at the core have been prepared. Flexible benzyl aryl ether dendrimers 1a-e were obtained in good yields by direct alkylation of diphenolic azobenzene 3 with benzyl aryl ether dendrons [G-n]-Br (n = 0-4). In rigid dendrimers 2a-e, the azobenzene configurational switch was linked to phenylacetylene dendrons through acetylenic linkages to maintain the shape-persistent nature of these dendrimers. A comparison of these two different classes of dendrimers with azobenzene cores reveals a difference in the properties of the photochromic moiety upon dendritic incorporation as well as a significant difference in the photomodulation of dendrimer properties. The E → Z photoisomerization quantum yield decreased markedly with increasing generation for dendrimers 1a-e but only slightly for dendrimers 2a-e. However, increasing generation did not significantly alter thermal isomerization kinetics or activation barriers. The hydrodynamic volumes of azobenzene-containing dendrimers 2b-e were significantly modulated when the azobenzene unit is subjected to irradiation, while those of dendrimers 1b-e were only slightly affected.
AB - Two analogous classes of dendrimers with a single azobenzene moiety at the core have been prepared. Flexible benzyl aryl ether dendrimers 1a-e were obtained in good yields by direct alkylation of diphenolic azobenzene 3 with benzyl aryl ether dendrons [G-n]-Br (n = 0-4). In rigid dendrimers 2a-e, the azobenzene configurational switch was linked to phenylacetylene dendrons through acetylenic linkages to maintain the shape-persistent nature of these dendrimers. A comparison of these two different classes of dendrimers with azobenzene cores reveals a difference in the properties of the photochromic moiety upon dendritic incorporation as well as a significant difference in the photomodulation of dendrimer properties. The E → Z photoisomerization quantum yield decreased markedly with increasing generation for dendrimers 1a-e but only slightly for dendrimers 2a-e. However, increasing generation did not significantly alter thermal isomerization kinetics or activation barriers. The hydrodynamic volumes of azobenzene-containing dendrimers 2b-e were significantly modulated when the azobenzene unit is subjected to irradiation, while those of dendrimers 1b-e were only slightly affected.
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U2 - 10.1021/ja036418p
DO - 10.1021/ja036418p
M3 - Article
C2 - 14971953
AN - SCOPUS:1242297021
VL - 126
SP - 2181
EP - 2185
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 7
ER -