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Influence of weaker interactions on the self-assembly of rigid molecular scaffolds based on tetraarylbimesityls

机译：弱相互作用对基于四芳基二甲基苯乙烯的刚性分子支架自组装的影响

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We have explored how weak interactions would manifest in three-dimensional (313) rigid scaffolds based on tetrarylbimesityls in which the close packing is likely to be more decisive. While the crystal structure of tetrapyridyl bimesityl (3,3',5,5'-tetrakis(4-pyridyl)bimesityl, 2) is found to be a close-packed one devoid of any perceptible interactions, that of 3,3',5,5'-tetrakis(3-pyridyl)bimesityl (1) is found to reveal a novel ring motif based on C-H center dot center dot center dot N hydrogen bonds, which serves to organize the molecules into a cubic alpha-Po-like network. The cyano-substituted derivative (3,3',5,5'-tetrakis(4-cyanophenyl)bimesityl, 3) is found to exhibit a helical organization as a result of C-H center dot center dot center dot N interactions and electrophile-nucleophile type pairing. Evidently, the interactions due to groups that interact weakly appear to be exploited in the crystal packing of 3D scaffolds only when their existence can be accommodated by a molecular packing that leads to overall crystal lattice stabilization as in 1 and 3. The crystal structures of 1 and 2 suggest a strong dependence on the location of weakly interacting sites. In the crystal structures of 3D rigid scaffolds, the close packing appears to dictate the manifestation or otherwise of the weak interactions and their association patterns/motifs.
机译：我们已经研究了在基于四丙烯腈的三维（313）刚性支架中弱相互作用将如何表现出来，其中紧密堆积可能更具决定性。虽然发现四吡啶基双甲双咪唑（3,3'，5,5'-四（4-吡啶基）双甲乙菲，2）的晶体结构是紧密堆积的，没有任何可察觉的相互作用，但3,3'的晶体结构，发现5,5'-四（3-吡啶基）二甲酸酯基（1）揭示了一个基于CH中心点中心点中心点N个氢键的新型环基序，该基序可将分子组织成立方α-Po-like网络。由于CH中心点中心点中心点中心点N相互作用和亲电子亲核体，氰基取代的衍生物（3,3'，5,5'-四（4-氰基苯基）二甲硅烷基1，3）显示出螺旋结构。类型配对。显然，仅当3D支架的存在可以被分子堆积（如1和3所示）导致整体晶格稳定的分子容纳时，弱相互作用基团的相互作用才似乎在3D支架的结晶堆积中得到利用。1的晶体结构和2表明强烈依赖弱相互作用的网站的位置。在3D刚性支架的晶体结构中，紧密堆积似乎决定了弱相互作用及其关联模式/基元的表现或其他。

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