Sebastián Rosa-María, Blais Jean-Claude, Caminade Anne-Marie, Majoral Jean-Pierre
Laboratoire de Chimie de Coordination, CNRS 205 route de Narbonne, 31077 Toulouse Cedex 04 (France) Fax: (+33) 5-61-55-30-03.
Chemistry. 2002 May 3;8(9):2172-83. doi: 10.1002/1521-3765(20020503)8:9<2172::AID-CHEM2172>3.0.CO;2-G.
We describe the synthesis of three series of phosphorus-containing dendrimers having azobenzene derivatives specifically placed at some generations in the interior and/or on the surface. The largest compound obtained possesses 48 azobenzene groups on the surface. Irradiation at 350 nm induces isomerization of the azobenzene groups from the E form to the Z form, whatever their location. The thermal back-isomerization to the E form in the dark at room temperature was observed in all cases. The kinetics of this Z-->E back-isomerization was studied in several cases; the rate is not dependent on the number of azobenzene units or of the generation, when the azobenzene groups are linked to the surface of the dendrimer. A different behavior was observed when the azobenzene groups were located within the framework of the dendrimer.
我们描述了三个系列含磷树枝状大分子的合成，这些树枝状大分子在某些代数的内部和/或表面特意引入了偶氮苯衍生物。所得到的最大化合物在表面具有48个偶氮苯基团。无论偶氮苯基团位于何处，在350 nm处进行辐照都会诱导其从E型异构化为Z型。在所有情况下均观察到在室温黑暗条件下向E型的热逆向异构化。在几种情况下研究了这种Z→E逆向异构化的动力学；当偶氮苯基团连接到树枝状大分子表面时，速率不依赖于偶氮苯单元的数量或代数。当偶氮苯基团位于树枝状大分子的骨架内时，观察到了不同的行为。
