Inducing Social Self-Sorting in Organic Cages To Tune The Shape of The Internal Cavity.
Inducing Social Self-Sorting in Organic Cages To Tune The Shape of The Internal Cavity.
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DOI：
10.1002/anie.202007571
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发表时间：
2020-09-14
期刊：
影响因子：
--
通讯作者：
Slater AG
中科院分区：
文献类型：
--
作者：
Abet V;Szczypiński FT;Little MA;Santolini V;Jones CD;Evans R;Wilson C;Wu X;Thorne MF;Bennison MJ;Cui P;Cooper AI;Jelfs KE;Slater AG
许多有趣的目标客体分子具有低对称性，但大多数合成主体的方法都会产生高度对称的胶囊。因此，需要产生较低对称性孔的方法以使主体-客体复合物中的结合亲和力最大化。在本文中，我们使用四醛结构单元与环己二胺的混合物来获得低对称性亚胺笼。低能笼是否被隔离可以从计算模型中观察到的热力学偏好正确预测。观察到的结构的稳定性取决于醛结构单元的几何匹配。一种弯曲的醛由于不能组装成高对称性笼而突出，并且当与线性醛组合时，相同的醛产生低对称性社会自分类笼。我们利用这一发现来合成一系列含有杂原子的低对称笼，说明通过计算预测和自分选可以可靠地访问不同几何形状和表面化学性质的孔。 一个不断扩展的形状的海洋：实验-计算相结合的方法使得能够从四醛结构单元的混合物合成低对称性亚胺笼。应用这种“社会自分选”方法来获得一系列含有杂原子的新笼，表明可以可靠地接近不同几何形状和表面化学性质的孔。
Many interesting target guest molecules have low symmetry, yet most methods for synthesising hosts result in highly symmetrical capsules. Methods of generating lower symmetry pores are thus required to maximise the binding affinity in host–guest complexes. Herein, we use mixtures of tetraaldehyde building blocks with cyclohexanediamine to access low‐symmetry imine cages. Whether a low‐energy cage is isolated can be correctly predicted from the thermodynamic preference observed in computational models. The stability of the observed structures depends on the geometrical match of the aldehyde building blocks. One bent aldehyde stands out as unable to assemble into high‐symmetry cages‐and the same aldehyde generates low‐symmetry socially self‐sorted cages when combined with a linear aldehyde. We exploit this finding to synthesise a family of low‐symmetry cages containing heteroatoms, illustrating that pores of varying geometries and surface chemistries may be reliably accessed through computational prediction and self‐sorting. A sea of expanding shapes: A combined experimental–computational approach enabled the synthesis of low‐symmetry imine cages from mixtures of tetraaldehyde building blocks. This “social self‐sorting” approach was applied to obtain a family of new cages containing heteroatoms, showing that pores of varying geometries and surface chemistries may be reliably accessed.
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