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Synthesis and Binding Properties of a Tren-Capped Hexahomotrioxacalix[3]arene.
ChemPhysChem ( IF 2.3 ) Pub Date : 2019-12-11 , DOI: 10.1002/cphc.201900951 Sara Zahim 1 , Daniela Ajami 1 , Pascal Laurent 2 , Hennie Valkenier 3 , Olivia Reinaud 4 , Michel Luhmer 5 , Ivan Jabin 1
ChemPhysChem ( IF 2.3 ) Pub Date : 2019-12-11 , DOI: 10.1002/cphc.201900951 Sara Zahim 1 , Daniela Ajami 1 , Pascal Laurent 2 , Hennie Valkenier 3 , Olivia Reinaud 4 , Michel Luhmer 5 , Ivan Jabin 1
Affiliation
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The straightforward synthesis of a new hexahomotrioxacalix[3]arene‐based ligand capped by a tren subunit was developed and the binding properties of the corresponding zinc complex were explored by NMR spectroscopy. Similarly to the closely related calix[6]tren‐based systems, the homooxacalixarene core ensures the mononuclearity of the zinc complex and the metal center displays a labile coordination site for exogenous guests. However, very different host–guest properties were observed: i) in CDCl3, the zinc complex strongly binds a water molecule and is reluctant to recognize other neutral guests, ii) in CD3CN, the exo‐coordination of anions prevails. Thus, in strong contrast to the calix[6]tren‐based systems, the coordination of neutral guests that thread through the small rim and fill the polyaromatic cavity was not observed. This unique behaviour is likely due to the fact that the 18‐membered ethereal macrocycle is too small to let a molecule threading through it. This work illustrates the key role played by the second coordination sphere in the binding properties of metal complexes.
中文翻译：
ren封的六亚甲基三氧杂ox [3]芳烃的合成及结合性能。
开发了由tren亚基封端的新的基于六高三氧杂acalix [3]亚芳基的配体的直接合成方法，并通过NMR光谱研究了相应锌配合物的结合特性。与紧密相关的基于杯[6] tren的系统相似，高草六氢芳烃核心确保了锌络合物的单核化，并且金属中心对外来宾显示出不稳定的配位位点。但是，观察到非常不同的宿主-客体特性：i）在CDCl 3中，锌络合物牢固结合水分子，不愿识别其他中性客体，ii）在CD 3中CN，阴离子的配位反应占优势。因此，与基于杯[6] tren的系统形成强烈对比，未观察到穿过小轮缘并填充多芳烃腔的中性客体的协调。这种独特的行为可能是由于18元醚空环太小而无法让分子穿过它的事实。这项工作说明了第二配位领域在金属配合物的结合特性中所起的关键作用。
更新日期：2019-12-11
中文翻译：
ren封的六亚甲基三氧杂ox [3]芳烃的合成及结合性能。
开发了由tren亚基封端的新的基于六高三氧杂acalix [3]亚芳基的配体的直接合成方法，并通过NMR光谱研究了相应锌配合物的结合特性。与紧密相关的基于杯[6] tren的系统相似，高草六氢芳烃核心确保了锌络合物的单核化，并且金属中心对外来宾显示出不稳定的配位位点。但是，观察到非常不同的宿主-客体特性：i）在CDCl 3中，锌络合物牢固结合水分子，不愿识别其他中性客体，ii）在CD 3中CN，阴离子的配位反应占优势。因此，与基于杯[6] tren的系统形成强烈对比，未观察到穿过小轮缘并填充多芳烃腔的中性客体的协调。这种独特的行为可能是由于18元醚空环太小而无法让分子穿过它的事实。这项工作说明了第二配位领域在金属配合物的结合特性中所起的关键作用。
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