Matsumoto Mutsuyoshi, Nakazawa Takahiro, Mallia V Ajay, Tamaoki Nobuyuki, Azumi Reiko, Sakai Hideki, Abe Masahiko
Nanotechnology Research Institute, National Institute of Advanced Industrial Science and Technology, AIST Tsukuba Central 5-2, 1-1-1 Higashi, Tsukuba 305-8565, Japan.
J Am Chem Soc. 2004 Feb 4;126(4):1006-7. doi: 10.1021/ja038844g.
We have found a thermal hysteresis in the photoresponsivity of a Langmuir film for the first time. The Langmuir film of an amphiphilic spiropyran, 1',3'-dihydro-3',3'-dimethyl-6-nitro-1'-octadecyl-8-(docosanoyloxymethyl)spiro[2H-1-benzopyran-2,2'-(2H)-indole] (SP) was fabricated at 13 degrees C at 10 mN m-1, followed by heating to a given temperature. UV irradiation of this film caused only the isomerization of SP to the corresponding merocyanine (MC) up to 29 degrees C. Light-induced J-aggregation of MC occurred at 30 degrees C. On the other hand, once the film was heated to 30 degrees C, light-induced J-aggregation was observed down to 27 degrees C. The hysteresis should be related with the phase transitions that occur in the bulk of SP at similar temperatures. No significant morphological change occurred by light-induced J-aggregation in the Langmuir-Blodgett (LB) film of SP by the present method, in contrast to the case of the LB films fabricated under isothermal conditions at 30 degrees C. This feature enabled us to pattern the LB film with J-aggregate of MC by UV irradiation through a photomask of lines with a width of 5 mum each.
我们首次在朗缪尔膜的光响应性中发现了热滞现象。两亲性螺吡喃1',3'-二氢-3',3'-二甲基-6-硝基-1'-十八烷基-8-(二十二烷酰氧基甲基)螺2H-1-苯并吡喃-2,2'-(2H)-吲哚的朗缪尔膜在13℃、10 mN m-1的条件下制备,随后加热至给定温度。在29℃以下,对该膜进行紫外线照射仅导致SP异构化为相应的部花青(MC)。在30℃时发生了光诱导的MC的J-聚集。另一方面,一旦将膜加热到30℃,在27℃时也观察到了光诱导的J-聚集。这种滞后现象应与在相似温度下SP本体中发生的相变有关。与在30℃等温条件下制备的LB膜的情况相比,通过本方法在SP的朗缪尔-布洛杰特(LB)膜中,光诱导的J-聚集没有引起明显的形态变化。这一特性使我们能够通过宽度为5μm的线的光掩模,通过紫外线照射对LB膜进行MC的J-聚集体图案化。