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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Synthesis and structural characterization of anion complexes with azacalix[2]dipyrrolylmethane: effect of anion charge on the conformation of the macrocycle
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Synthesis and structural characterization of anion complexes with azacalix[2]dipyrrolylmethane: effect of anion charge on the conformation of the macrocycle

机译：氮杂杯[2]二吡咯烷基甲烷阴离子配合物的合成与结构表征：阴离子电荷对大环构象的影响

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摘要

Tetrahomodiazacalix[2]dipyrrolylmethane 1, [-CH2(C4H3N)CR2(C4H3N)CH2N(Me)-](2) an expanded version of the calix[4]pyrrole system, has the tendency to change its ring conformation (1,3- alternate) upon anion binding analogous to calix[4]pyrrole. However, owing to its tertiary amine nitrogen atoms in the ring, it can be protonated and becomes a powerful cationic receptor for anions, besides its inherent hydrogen bonding features. Macrocycle 1 binds with a series of monoanions BF4-, Cl-, PhCOO- and ClO4-, and their X-ray structures showed that the ring conformation constitutes the 1,2-alternate form. Upon binding with dianions SO42-, CrO42-, SiF62- and S2O32-, the ring conformation changes to the cone conformation. The intermediate partial cone conformation results for complexes with NO3- and Cr2O72- ions. The change in the orientation of the pyrrole NH groups depending on the charge of the anion demonstrates the flexibility of the macrocycle and the dicationic macrocycle stabilizes the anions via both hydrogen bonding and electrostatic interactions.
机译：四苯并二氮杂螺[2]二吡咯基甲烷1，[-CH2（C4H3N）CR2（C4H3N）CH2N（Me）-]（2）杯[4]吡咯系统的扩展版，倾向于改变其环构型（1,3 -交替地）与杯[4]吡咯类似的阴离子结合。但是，由于其环中的叔胺氮原子，除其固有的氢键键合特性外，它还可被质子化并成为强大的阴离子阳离子接收器。大环化合物1与一系列单阴离子BF4-，Cl-，PhCOO-和ClO4-结合，它们的X射线结构表明环构象构成1,2-交替形式。与二价阴离子SO42-，CrO42-，SiF62-和S2O32-结合后，环构象变为圆锥构象。与NO3-和Cr2O72-离子形成配合物的中间部分圆锥构象结果。取决于阴离子的电荷，吡咯NH基团的方向变化证明了大环的柔韧性，而双阳离子大环通过氢键和静电相互作用稳定了阴离子。

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