Selective endo and exo binding of mono- and ditopic ligands to a rhomboidal diporphyrin prism.
Selective endo and exo binding of mono- and ditopic ligands to a rhomboidal diporphyrin prism.
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DOI：
10.1002/anie.201501359
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发表时间：
2015-06
影响因子：
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通讯作者：
G. Jayamurugan;D. Roberts;Tanya K. Ronson;J. Nitschke
中科院分区：
文献类型：
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作者：
G. Jayamurugan;D. Roberts;Tanya K. Ronson;J. Nitschke
由于空间位阻因素，铜（I）可以优先形成含有两个膦和两个氮供体的混配配合物。这种偏好被用来指导卟啉面临的菱形棱镜具有两个平行的tetrakis（4-iminopyridyl）porphyrinatozinc（II）面连接8个1，4-双（二苯基膦基）苯柱的自组装。Cu（I）离子的配位偏好和配体的几何形状一起产生卟啉锌（II）面的滑动共面取向。这种取向使得能够选择性地包封3，3 '-联吡啶（bipy），其桥接平行卟啉的Zn（II）离子，而4，4'-联吡啶表现出较弱的卟啉表面的外部配位。相反，与2，2 '-bipy的反应导致四位卟啉配体的置换和[{（2，2'-bipy）Cu（I）}2（二膦）2 ]的形成。联吡啶异构体与系统的相互作用强度不同，这使得可以解释一个层次结构，即4，4 '-bipy可以被3，3'-bipy取代，3，3 '-bipy又被2，2'-bipy取代。
Copper(I) can preferentially form heteroleptic complexes containing two phosphine and two nitrogen donors due to steric factors. This preference was employed to direct the self-assembly of a porphyrin-faced rhomboidal prism having two parallel tetrakis(4-iminopyridyl)porphyrinatozinc(II) faces linked by eight 1,4-bis(diphenylphosphino)benzene pillars. The coordination preferences of the Cu(I) ions and geometries of the ligands come together to generate a slipped-cofacial orientation of the porphyrinatozinc(II) faces. This orientation enables selective encapsulation of 3,3'-bipyridine (bipy), which bridges the Zn(II) ions of the parallel porphyrins, whereas 4,4'-bipy exhibits weaker external coordination to the porphyrin faces. Reaction with 2,2'-bipy, by contrast, results in the displacement of the tetratopic porphyrin ligand and formation of [{(2,2'-bipy)Cu(I) }2 (diphosphine)2 ]. The differing strengths of interactions of bipyridine isomers with the system allows for a hierarchy to be deciphered, whereby 4,4'-bipy may be displaced by 3,3'-bipy, which in turn is displaced by 2,2'-bipy.