干旱区生态环境知识资源中心

We report here the synthesis of:a new Chiral Zn(II) bisporphyrin tweaer in which two achiral Zn(11); porphyrin moieties are covalently linked by (1R;2R)-diphenylethylenediamine, which produces a strong chiral field around the porphyrin moieties. The chiral tweezer exhibits not only intensity modulation in UV-vis and CL) exciton couplets but also a dramatic change, namely, the inversion in the sign of the interporphyrin helicity upon binding of achiral diamines of varying lengths. The stoichiometry-controlled formation of a 1:1 sandwich complex followed by a 1:2 open complex was realized with smaller achiral diamines (n: 2-5) fat their low and high concentration regions, respectively, leading to two-step inversion of chirality. With longer achiral diarilines (n: 6-8), however, only 1:1 sandwich complexes are formed with no change of sign in the CD couplet. As compared to a 1:2 open complex, a 1:1 sandwich complex shows an enhanced CD response as two porphyrin units come closer in space. Structural insights of the host-guest complexes have been obtaineds pectrostopically along with molecular mechanics minimizations with the newly implemented OPLS-3 force field followed by geometry optimization using density functional theory of the most stable conformer. The amide bridge in the Zn(II) bisporphyrin has a low rotational barrier, which provides conformational flexibility to change interporphyrin helicity between 1:1 arid 1:2 binding,depending on the size of the achiral guests, in order to minimize host-guest steric interactions.