THE VERIFICATION OF THE INTERACTION BETWEEN C-F UNIT AND METAL CATIONS OR ORGANIC CATIONS

通过观察金属阳离子与笼形化合物1和2(以6个氟苯单位（1)或4个氟苯单位和2个二乙烯基单位(2)为供体原子）之间的核磁共振波谱变化和络合研究，研究了C-F…M^+相互作用。结果，检测到与1和2形成配合物的所有金属阳离子的相互作用。1和2配合物的稳定性是由金属阳离子的性质（离子半径和水解程度）决定的，而不是由阳离子的硬-软性质决定的。T1^+∧1和La^<3+>∧2的晶体学分析提供了结构信息（原子间距离和键角），结合强度C-F…M^+、O…M^+和N…M^+根据结构数据通过布朗方程估计。在复合体T1^+∧1中观测到较短的C-F…T1^+(2.952 ~ 3.048)距离。与meta -free化合物相比，配合物T1^+∧1和La^<3+>∧2中的C-F键长度被拉长。有趣的是，在La^<3+>∧2中，没有包括水分子在内的溶剂分子与La^<3+>∧2配位。根据x射线晶体学分析数据计算了阳离子-偶极相互作用的稳定能，结果与【-！【水平分三角形】解中H值的估计。因此，C-F…M^+相互作用可以用阳离子-偶极子相互作用来表示。这一结果解释了以氟原子为硬供体的化合物1能强结合Ag^+和T1^+等软金属的事实。与醚氧或胺氮相比，氟苯单元的给电子能力较差，因此C-F…M^+中的配位键比例较小。随着M^+与宿主1和宿主2之间的络合作用，观察到^1H、^<13>C和^<19>F核磁共振谱发生了特殊而显著的变化。这些光谱特征是研究C-F…M^+相互作用的重要工具。此外，在室温下，在T1^+∧1,2中观察到F…T1^+自旋耦合（T1^+∧1的J_<F-T1> = 2914 Hz， T1^+∧2的J_<F-T1> = 4558 Hz），这些是相互作用的明确证据。少

The C-F…M^+ interaction was investigated by observation of the NMR spectroscopic changes and complexation studies between metal cations and the cage compounds 1 and 2 which have six fluorobenzene units (1) or four fluorobenzene units and two diethyleneoxa units (2) as donor atoms. As a result, the interaction was detected with all of the metal cations which form complexes with 1 and 2. The stability of the complexes of 1 and 2 was determined by the properties of the metal cations (ionic radii and degree of hydrolysis), not by the hard-soft nature of the cations. Crystallographic analyses of T1^+ ⊂ 1 and La^<3+> ⊂ 2 provided structural information (interatomic distances and bond angles), and the bond strengths, C-F…M^+, O…M^+, and N…M^+, were estimated by Brown's equation based on the structural data. Short C-F…T1^+ (2.952 〜 3.048) distances were observed in the complex T1^+ ⊂ 1. The C-F bond lengths in the complexes, T1^+ ⊂ 1 and La^<3+> ⊂ 2, are elongated compared to those of the meta … More l-free compounds. Interestingly, no solvent molecules including water molecules were coordinated to La^<3+> in the La^<3+> ⊂ 2. The stabilization energy of cation-dipole interaction was calculated based on the data from X-ray crystallographic analysis, and it is roughly consistent with the【-!【horizontally divided triangle】】H values estimated in solution. Thus, the C-F…M^+ interaction can be expressed by the cation-dipole interaction. This result explains the fact that compound 1 which has fluorine atom as hard donor strongly binds soft metals such as Ag^+ and T1^+. Furthermore, it was concluded that the fluorobenzene unit has a poor electron-donating ability compared to that of ether oxygen or amine nitrogen, and thus the ratio of the coordination bond in C-F…M^+ is small. The specific and remarkable changes in the ^1H, ^<13>C, and ^<19>F NMR spectra were observed accompanied by the complexation between M^+ and the hosts 1 and 2. These spectral features are important tools for the investigation of the C-F…M^+ interaction. Furthermore, F…T1^+ spin couplings were observed at room temperature in the T1^+ ⊂ 1, 2 (J_<F-T1> = 2914 Hz for T1^+ ⊂ 1 and 4558 Hz for T1^+ ⊂ 2), and these are clear and definitive evidence of the interaction. Less