Construction of functional supramolecules based on the electronic properties of heteroatoms and nonalternant conjugation

由1，3-二氯-2-天青烯基衍生的非选择性有机配体首次被引入到铋和锑的中心。二氟化氙将天青基铋转变为五配位二氟化物，促进了天青核的π极化，这是溶液中颜色的变化以及核磁共振谱的化学位移的变化。在锑同系物中也观察到了类似的趋势。对(1，3-二氯-2-天青基)二氟化铋的X-射线结晶学研究表明，分子间的π-π堆积是通过五元环与七元环相互作用在天青基之间发生的。这可能反映了二氟化物的更极化的天青基，这加强了堆积卤素[interaction.(1，3-Dihalo-2-azulenyl)diphenylphosphines=Cl，Br]的合成，并研究了非取代的天青基对这些膦的反应性和性质的影响，并与第15族同系物的影响进行了比较。非交替共轭的电子结构受磷原子价态变化的影响很大。因此，双氧水氧化偶氮苯基二苯基膦时，颜色发生了显著的变化，从绿色变为蓝色，得到了相应的膦氧化物。~&lt；13&gt；c核磁共振研究表明，与母体膦相比，膦氧化物的天青基上的π极化增强，但程度不如铋和锑体系中观察到的那样明显。蔚蓝基氧化膦在晶体中具有从头到尾的π-π堆积，反映了磷中心高氧化状态下π极化的增强。

A nonaltemant organyl ligand derived from azulene, a 1,3-dichloro-2-azulenyl group, is introduced for the first time into the bismuth and antimony center. Conversion of the azulenylbismuthanes into the pentacoordinated difluorides by xenon difluoride promotes the π-polarization of the azulene nucleus, which is detected as a color change in solution as well as changes in the chemical shifts of the ^<13>C NMR spectra. Similar tendency is observed in the antimony congeners. The X-ray crystallographic study of (1,3-dichloro-2-azulenyl)diphenylbismuth difluoride reveals that the intermolecular π-π stacking takes place between the azulenyl groups through the interaction of the five-membered ring with the seven-membered ring. This may reflect the more polarized azulenyl group of the difluorides, which strengthens the stacking interaction.(1,3-Dihalo-2-azulenyl)diphenylphosphines [halogen=Cl,Br] have been synthesized, and the effect of the nonaltemant azulenyl group on the reactivity and properties of these phosphines has been studied in comparison with that of the group 15 congeners. The electronic structure of the nonalternant conjugation is dramatically affected by the change in the valency at the phosphorus. Thus, oxidation of the azulenyldiphenylphosphines with hydrogen peroxide proceeded with a dramatic color change from green to blue, giving the corresponding phosphine oxides. The ^<13>C NMR study shows the enhanced π-polarization in the azulenyl group of the phosphine oxides compared to that of the parent phosphines, but the degree is not as marked as that observed in the bismuth and antimony systems. Azulenylphosphine oxide has head-to-tail π-π stacking in crystals, reflecting the enhanced π-polarization in the high oxidation state of the phosphorus center.