Influence of receptor flexibility on intramolecular H-bonding interactions.
Influence of receptor flexibility on intramolecular H-bonding interactions.
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受体灵活性对分子内氢键相互作用的影响。
DOI：
10.1039/c5ob00805k
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发表时间：
2015
影响因子：
3.2
通讯作者：
Sun H
中科院分区：
文献类型：
--
作者：
Sun H
合成了一系列四苯基锌卟啉的阻转异构体，并将其用作超分子受体。通过在苯基上安装邻氯取代基来限制围绕卟啉-meso苯基键的旋转。氯取代基允许阻转异构体的色谱分离，其在室温下不互变。卟啉的meso苯基也配备了苯酚基团，这导致形成分子内氢键时，锌卟啉结合到吡啶配体配备酯或酰胺侧臂。与相应的未取代的卟啉，这是更灵活的构象锁定的氯卟啉的吡啶配体的结合进行了比较。测定了150个锌卟啉吡啶配合物在甲苯和1，1，2，2-四氯乙烷（TCE）两种不同溶剂中的缔合常数。这些关联常数，然后被用来构建120个化学双突变体的循环，以量化氯取代的影响的自由能之间形成的卟啉的酚侧臂和吡啶配体的酯或酰胺侧臂的分子内H-键。构象限制导致一些复合物的稳定性增加，而另一些复合物的稳定性降低，分子内氢键的自由能贡献为−5至+6 kJ mol−1。
Atropisomers of a series of zinc tetraphenyl porphyrins were synthesized and used as supramolecular receptors. Rotation around the porphyrin-meso phenyl bonds is restricted by installing ortho-chlorine substituents on the phenyl groups. The chlorine substituents allowed chromatographic separation of atropisomers, which did not interconvert at room temperature. The porphyrin meso phenyl groups were also equipped with phenol groups, which led to the formation of intramolecular H-bonds when the zinc porphyrins were bound to pyridine ligands equipped with ester or amide side arms. Binding of the pyridine ligands with the conformationally locked chloroporphyrins was compared with the corresponding unsubstituted porphyrins, which are more flexible. The association constants of 150 zinc porphyrin–pyridine complexes were measured in two different solvents, toluene and 1,1,2,2-tetrachloroethane (TCE). These association constants were then used to construct 120 chemical double mutant cycles to quantify the influence of chlorine substitution on the free energy of intramolecular H-bonds formed between the phenol side arms of the porphyrins and the ester or amide side arms of the pyridine ligands. Conformational restriction leads to increases in the stability of some complexes and decreases in the stability of others with variations in the free energy contribution due to intramolecular H-bonding of −5 to +6 kJ mol−1.
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外围拥挤的卟啉中不寻常的芳基卟啉旋转屏障。
DOI：
10.1021/ic010958a
发表时间：
2003
期刊：
Inorganic chemistry.
影响因子：
--
作者：
Medforth,CraigJ;Haddad,RaidE;Muzzi,CinziaM;Dooley,NealR;Jaquinod,Laurent;Shyr,DavidC;Nurco,DanielJ;Olmstead,MarilynM;Smith,KevinM;Ma,Jian-Guo;Shelnutt,JohnA
通讯作者：
Shelnutt,JohnA
影响因子：
8.4
作者：
Hunter, Christopher A.;Misuraca, Maria Cristina;Turega, Simon M.
通讯作者：
Turega, Simon M.
影响因子：
15
作者：
Gestwicki, JE;Cairo, CW;Kiessling, LL
通讯作者：
Kiessling, LL
影响因子：
15
作者：
Hunter, Christopher A.;Misuraca, Maria Cristina;Turega, Simon M.
通讯作者：
Turega, Simon M.
5,10,15,20-四(2,6-二氯-3-氨磺酰基-苯基)卟啉的阻转异构体
影响因子：
1.5
作者：
Ana S Ressurreição;M. Piñeiro;L. Arnaut;A. Gonsalves
通讯作者：
A. Gonsalves