Picosecond-Millisecond Dynamics of Mlecular Recognition Processes

合成了几种光化学受体，并在稳态光谱和时间分辨光谱的基础上研究了它们的分子或离子识别过程。首次合成了2，2‘-联吡啶3，3’-冠醚结构的Ru(II)配合物(CE-bpy)：Ru(Bpy)_2(CE-bpy)。当加入钠或钾离子时，络合物的发射光谱发生很大变化，而吸收光谱对离子几乎不敏感。用钠离子在乙腈中进行发射滴定，测得络合常数为10^3M^~(-1)~(-1)。离子的存在也影响了络合物的发射动力学。杯芳烃四磺酸盐作为反离子的Ru(II)络合物(RUB-CALX)：将杯芳烃四磺酸盐加入三(，2‘-联吡啶)Ru(II)的水溶液中，得到纯的RUB-CALIX晶体。在溶液中。在钠，MAGN…的存在下，杂化络合物的发射强度增加更多的铯，或铝离子。在无离子存在的情况下，橡胶与杯芳烃形成杂化络合物，其激发态被杯芳烃部分猝灭。在An*n存在的情况下，反阳离子交换继续进行，因此，自由摩擦的量增加。排放动力学实验很好地解释了这些过程。分子铰链的光化学：哈密尔顿等人首次报道的“分子铰链”。通过吸收光谱和荧光光谱对其进行了重新研究。当分子Inge与丁基胸腺嘧啶相互作用时，铰链的吸收光谱和荧光光谱都发生了显著的变化。荧光动力学显示了宿主与客体之间的静态相互作用。巴比图衍生物氢键相互作用的光谱研究：合成了具有芳香烃基团的巴比图衍生物，并研究了它们与二氨基吡啶在乙腈和四氢呋喃中的氢键作用。较少

Several photochemical receptors were synthesized and their molecular or ion recognition processes were studied on the basis of steady-state and time-resolved spectroscopy.1). Ru (II) Complex Having Crown-Ether Moiety at 3, 3'-Positions of 2, 2'-Bipyridine (CE-bpy) : Ru (bpy)_2(CE-bpy) was synthesized for the first time. Upon addition of a sodium or pottasium ion, the emission spectrum of the complex varied considerably, while the absorption spectrum was almost insensitive to the ion. Emission titration by a sodium ion in acetinitrile demonstrated the association constant being 10^3 M^<-1>. Emission dynamics of the complex was also influened by the presence of the ion.2). Ru (II) Complex Having Calixarene Tetrasulfonate as Counter Cation (RuB-Calix) : Addition of calixarene tetrasulfonate into an aqueous solution of tris (, 2'-bipyridine) ruthenium (II) afforded pure RuB-Calix crystals. In solution. The emission intensity of the hybrid complex increased in the presence of a sodium, magn … More esium, or aluminum ion. In the absence of an ion, RuB and calixarene produced a hybrid complex and the excited state of RuB was quenched by the calixarene moiety. In the presence of an *n, counter cation exchange proceeds and, thus, the amount of free RuB increased. These processes were well explained by emission dynamic experiments.3). Photochemistry of Molecular Hinge : The "Molecular Hinge" first reported by Hamilton et al. was reinvestigated by absorption and fluorescence spectroscopy. Upon hudrogen bonding interaction between the molecular inge and butylthymine, both absorption and fluorescence spectra of the hinge changed dramatically. Fluorescence dynamic demonstrated static interaction between the host and guest.4). Spectroscopic Study on Hydrogen Bonding Interaction of Barbitul derivatives : Baribitul derivatives having an aromatic hydrocarbon moiety such as pyrene, anthracene, or N-ethylcarbazole were synthesized and their hydrogen bonding interaction with diaminopyridine were studied in acetonitrile and THF. Less