Iodine-assisted assembly of helical coordination polymers of cucurbituril and asymmetric copper(ii) complexes
Iodine-assisted assembly of helical coordination polymers of cucurbituril and asymmetric copper(ii) complexes
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DOI：
10.1002/anie.200463071
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发表时间：
2005-01-01
影响因子：
16.6
通讯作者：
Yamauchi, O
中科院分区：
文献类型：
--
作者：
Zhang, F;Yajima, T;Yamauchi, O
安吉街3469号2005，117，3468 - 3473 www. angewandte。de 2005 Wiley-VCH Verlag GmbH & Co. KGaA，魏因海姆配位的芳环分别为130.3和106.18。正是这些离散的和适当的斜弯曲构象允许不对称的形状匹配，从而导致离散的螺旋结构（图3和图4）。倾斜弯曲的构象是让人想起甲状腺激素，其内部和外部的酚环是不对称桥接的醚氧原子，而不是这里提出的络合物的铜离子。[3b]在配合物2中，带正电荷的P和M聚合物螺旋以相反的取向交替堆积（图3a），并组装成具有开放空腔的二维层结构。每个空腔由三个CB6对映体对的半壁组成，通过两个CB6对映体对的G3半甘脲环之间的形状匹配相互作用，环-环距离为3.29。最重要的是，每个开放腔保持同中心对称性，以相同的对称性紧密容纳一对[Cu（I2sal）（Hqs）] 2 π对映体。据我们所知，这是第一个例子的螺旋对映体主体-客体组装从一个不对称的过渡金属络合物阴离子（客体）和外壁的CB6分子内的空腔形成的阳离子聚集体（主机）通过不对称的形状匹配的相互作用。2中[Cu（I2sal）（Hqs）] 2 π的斜弯曲形式以这样的方式排列，即向内的I2sal和Hqs环面分别适合同一CB 6分子的单元G6和G5的半甘脲环。I2sal和Hqs外环面
3469 Angew. Chem. 2005, 117, 3468–3473 www. angewandte. de 2005 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim coordinated aromatic rings are 130.3 and 106.18, respectively. It is these discrete and properly skew-bent conformations that allow the asymmetric shape-matching and thus result in the discrete helical structures (Figures 3 and 4). The skew-bent conformations are reminiscent of that of thyroid hormones, whose inner and outer phenol rings are asymmetrically bridged by an ether oxygen atom instead of the CuII ion of the complexes presented here.[3b] In complex 2, the positively charged P and M polymer helices are alternately packed with opposite orientations (Figure3a) and assembled as a two-dimensional layer structure with open cavities. Each cavity is composed of the half walls of three CB6 enantiomer pairs through shapematching interactions between the G3 semi-glycoluril rings of two CB6 enantiomer pairs with a ring–ring distance of 3.29. Most importantly, each open cavity holds homocenter symmetry, tightly accommodating a pair of [Cu (I2sal)(Hqs)] 2À enantiomers in the same symmetry. To our knowledge, this is the first example of a helical enantiomeric host–guest assembly constructed from an asymmetric transition metal complex anion (guest) and the outer walls of CB6 molecules within the cavity-forming cation aggregates (host) through asymmetric shape-matching interactions. The skew-bent form of [Cu (I2sal)(Hqs)] 2À in 2 is arranged in such a way that the inward I2sal and Hqs ring faces fit to the semi-glycoluril rings of units G6 and G5, respectively, of the same CB6 molecule. The outward I2sal and Hqs ring faces