Influence of non-covalent preorganization on supramolecular effective molarities.
Influence of non-covalent preorganization on supramolecular effective molarities.
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非共价预组织对超分子有效摩尔浓度的影响。
DOI：
10.1039/c5ob00231a
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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
一个家庭的密切相关的锌卟啉-吡啶配合物被用来检查的影响，链接预组织超分子的有效摩尔形成分子内氢键。每个吡啶配体配备有含有两个氢键受体的侧链，一个在链的末端（末端），一个在链的中间（接头）。这些氢键受体与卟啉外围的苯酚氢键供体发生分子内相互作用。使用两种不同的氢键受体作为连接基团，以构建具有显著不同程度的预组织的框架：酯连接基团在60-70%的时间内占据氢键状态，而酰胺连接基团在90-100%的时间内占据氢键状态。因此，酰胺连接体提供比酯连接体显著更预组织的配体框架。使用32个化学双突变体循环对配体（酯和酰胺）上的末端H-键受体基团和卟啉酚基团之间的分子内H-键的有效摩尔浓度（EM）进行定量。EM的值与终端H-键受体的相互作用是独立的连接器H-键受体（弱键合酯或强键合酰胺）的性质，这表明，preorganization的连接器在这些系统中的螯合协同性没有影响。
A family of closely related zinc porphyrin–pyridine complexes were used to examine the influence of linker preorganization on supramolecular effective molarities for formation of intramolecular H-bonds. Each pyridine ligand was equipped with a side-chain containing two H-bond acceptors, one on the end of the chain (terminal) and one in the middle of the chain (linker). These H-bond acceptors make intramolecular interactions with phenol H-bond donors on the porphyrin periphery. Two different H-bonding acceptors were used as linker groups in order to construct frameworks with significantly different degrees of preorganization: ester linkers populate the H-bonded state 60–70% of the time, whereas amide linkers populate the H-bonded state 90–100% of the time. Thus the amide linkers provide a significantly more preorganised ligand framework than the ester linkers. Effective molarities (EM) for intramolecular H-bonds between the terminal H-bond acceptor groups on the ligands (esters and amides) and the porphyrin phenol groups were quantified using 32 chemical double mutant cycles. The values of EM for interactions with the terminal H-bond acceptors are independent of the nature of the linker H-bond acceptor (weakly bonded ester or strongly bonded amide), which indicates that preorganization of the linker has no effect on chelate cooperativity in these systems.
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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：
--
作者：
Hunter, CA;Tomas, S
通讯作者：
Tomas, S
影响因子：
15
作者：
Hunter, Christopher A.;Misuraca, Maria Cristina;Turega, Simon M.
通讯作者：
Turega, Simon M.
微波辅助无溶剂分子内 1,3-偶极环加成反应生成六氢苯并[4,3-b]吡咯：范围和局限性
DOI：
--
发表时间：
2007
期刊：
影响因子：
--
作者：
J. Pospíšil;M. Potáček
通讯作者：
M. Potáček
影响因子：
15
作者：
Chekmeneva, Elena;Hunter, Christopher A.;Turega, Simon M.
通讯作者：
Turega, Simon M.