Heterocorrole Conformations: Little Saddling, Much Ruffling.
Heterocorrole Conformations: Little Saddling, Much Ruffling.
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DOI：
10.1002/anie.201705551
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发表时间：
2017-08
影响因子：
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通讯作者：
J. Roesner;Birte Cordes;Stefan Bahnmüller;Gabor Homolya;Dimitri Sakow;Peter Schweyen;R. Wicht;M. Bröring
中科院分区：
文献类型：
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作者：
J. Roesner;Birte Cordes;Stefan Bahnmüller;Gabor Homolya;Dimitri Sakow;Peter Schweyen;R. Wicht;M. Bröring
10-制备并研究了在大环的10位上与氧、硫和硒以及与镍、铜和钯的二价离子的杂可咯配合物。重点研究了腐蚀型大环化合物中空穴尺寸与离子半径的尺寸匹配机制。一套完整的单晶X-射线分析数据显示，在所有情况下，但一个环收缩的四吡咯的N4结合位点大于所需的结合金属离子而不变形。通过M-N键长延长2.5- 3.2%的面内尺寸适应是有效的，对于具有更严重尺寸错配的那些化合物，大环的显著面外褶皱也是有效的。这种褶皱以前被排除在corroles之外，但显然是适应小中心离子的最有效机制。
10-Heterocorrole complexes with oxygen, sulfur, and selenium at position 10 of the macrocycle and with the divalent ions of nickel, copper, and palladium were prepared and investigated. The focus was set on the size adaptation and matching mechanisms of cavity size versus ionic radius in corrole-type macrocycles. A full set of single-crystal X-ray analytical data revealed that in all but one case the N4 binding site of the ring-contracted tetrapyrrole was larger than necessary to bind the metal ion without deformation. In-plane size adaptation through M-N bond-length elongation by 2.5-3.2 % was effective, as well as pronounced out-of-plane ruffling of the macrocycle for those compounds with a more severe size mismatch. Such ruffling had been excluded for corroles previously, but is apparently the most efficient mechanism to adapt to small central ions.