Fudickar Werner, Linker Torsten
Department of Chemistry, University of Potsdam, 14476 Potsdam, Germany.
Chemistry. 2006 Dec 13;12(36):9276-83. doi: 10.1002/chem.200600387.
The aliphatic anthracene compound 1 and the oligomeric anthracene 2 were synthesized. Thin films of 1 and 2 mixed with the sensitizers tetraphenylporphyrin (TPP) and methylene blue (MB) were irradiated with visible light in air. Upon formation of singlet oxygen, the anthracene units were converted quantitatively to the corresponding endoperoxides. Heating of the irradiated samples afforded the parent anthracenes with high yields. Here, we demonstrate that the kinetics and reversibility of this reaction strongly depend on the microenvironment of the anthracene groups in the two compounds. The photooxidation of thin films of 1 is accompanied by interesting changes in the morphology of the film and allows the first application of 1 as a nondestructive negative-tone photoresist for lithography and as an oxidizing ink. The morphology of 2 remained unchanged after photooxidation as a result of the stabilizing oligomer backbone. This stabilizing effect significantly improves the photochromic performance of 2. The reversibility of the photooxidation is very high (>90 %) for oligomeric films of 2 after several cycles of irradiation and heating. Decomposition of the anthracene and a loss of the activity of the sensitizer diminish slightly the performance of the monomeric species.
合成了脂肪族蒽化合物1和低聚蒽2。将1和2与敏化剂四苯基卟啉（TPP）和亚甲蓝（MB）混合形成的薄膜在空气中用可见光照射。单线态氧形成后，蒽单元定量转化为相应的内过氧化物。加热辐照后的样品可高产率得到母体蒽。在此，我们证明该反应的动力学和可逆性强烈依赖于这两种化合物中蒽基团的微环境。1的薄膜光氧化伴随着薄膜形态的有趣变化，并首次将1用作光刻的无损负性光刻胶和氧化油墨。由于低聚物主链具有稳定作用，2光氧化后形态保持不变。这种稳定作用显著提高了2的光致变色性能。经过几个辐照和加热循环后，2的低聚薄膜光氧化的可逆性非常高（>90%）。蒽的分解和敏化剂活性的丧失使单体物种的性能略有下降。
