Liu Yun-Long, Wang Wen-Jun, Gao Xue-Xi, Li Shu-Hong
School of Physical Science & Information Technology, Liaocheng University, Liaocheng 252059, China.
Guang Pu Xue Yu Guang Pu Fen Xi. 2008 Feb;28(2):422-5.
The configuration state and spectral properties of sandwiched thulium bisphthalocyanine (TmPc2) molecule in Langmuir films and Langmuir-Blodgett (LB) films were investigated by using the surface pressure-area (pi-A) isotherm and UV-Vis absorption spectra. The experimental results indicated that the sandwiched thulium bisphthalocyanine molecules form well-ordered stable monolayer films on the water/air interface, and the sandwiched thulium bisphthalocyanine molecules take the face to face orientation for the macrocycles and edge-on configuration in pure films, with the collapse pressure being 56 mN x m(-1). But the sandwiched thulium bisphthalocyanine molecules take the face-on configuration in the sandwiched thulium bisphthalocyanine films mixed with arachidic acid (AA), and the collapse pressure is more than 60 mN x m(-1). The sandwiched thulium bisphthalocyanine molecule could form well stable Langmuir films on sub-phase surface. The mixed TmPc2/arachidic acid not only could form well stable Langmuir films, but also could be transferred to solid substrate and deposited LB multilayers. In the chloroform solution and LB films of sandwiched thulium bisphthalocyanine, the UV-Vis absorption spectra have two absorption bands, namely Soret-bands and Q-bands. The electron orbit of sandwiched metal bisphthalocyanines was calculated by using absorption spectra VEH (Valence effective Hamiltonian) theory, and the electron transition orbit corresponding to the absorption peaks was analyzed. The Soret absorption band has two absorption peaks that are correlated with the electron orbital transitions of 184-187* and 178-186, and four absorption peaks of the Q absorption band are correlated with the electron orbital transitioned of 186-189*, 190* and 185-187*, 188*. In the LB films, the absorption peaks were red-shifted compared with those in the solution because of the interaction of molecules. The interaction of intra-layer molecules was stronger than that of interlayer molecules.
利用表面压力-面积(π-A)等温线和紫外-可见吸收光谱,研究了夹在中间的双酞菁铥(TmPc2)分子在朗缪尔膜和朗缪尔-布洛杰特(LB)膜中的构型状态和光谱性质。实验结果表明,夹在中间的双酞菁铥分子在水/空气界面上形成了有序稳定的单层膜,在纯膜中,夹在中间的双酞菁铥分子的大环呈面对面取向,边缘取向构型,崩塌压力为56 mN·m⁻¹。但夹在中间的双酞菁铥分子在与花生酸(AA)混合的夹在中间的双酞菁铥膜中呈面朝上构型,崩塌压力超过60 mN·m⁻¹。夹在中间的双酞菁铥分子可以在亚相表面形成稳定的朗缪尔膜。混合的TmPc2/花生酸不仅可以形成稳定的朗缪尔膜,还可以转移到固体基质上并沉积LB多层膜。在夹在中间的双酞菁铥的氯仿溶液和LB膜中,紫外-可见吸收光谱有两个吸收带,即索雷特带和Q带。利用吸收光谱VEH(价有效哈密顿量)理论计算了夹在中间的金属双酞菁的电子轨道,并分析了与吸收峰对应的电子跃迁轨道。索雷特吸收带的两个吸收峰与184-187和178-186的电子轨道跃迁相关,Q吸收带的四个吸收峰与186-189、190和185-187、188*的电子轨道跃迁相关。在LB膜中,由于分子间的相互作用,吸收峰相对于溶液中的吸收峰发生了红移。层内分子间的相互作用强于层间分子间的相互作用。