Molecular tectonics: chiral 1- and 2-D zinc coordination networks based on chiral porphyrins bearing pyridyl and ethynylpyridyl appended units
Molecular tectonics: chiral 1- and 2-D zinc coordination networks based on chiral porphyrins bearing pyridyl and ethynylpyridyl appended units
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DOI：
10.1039/c3nj00591g
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发表时间：
2013-10
影响因子：
3.3
通讯作者：
N. Marets;V. Bulach;M. W. Hosseini
中科院分区：
文献类型：
--
作者：
N. Marets;V. Bulach;M. W. Hosseini
设计了两个手性卟啉配体，在它们的相对的内消旋位置上带有两个附加的吡啶基或乙炔基吡啶基单元和手性基团。对于每种配体，合成两种对映异构体。在Zn（II）阳离子的存在下，手性配体在通过卟啉的四氮杂核结合金属中心时变成自互补的手性金属配体。由于自由配位的吡啶基单元和锌原子的存在，在同一实体内提供一个或两个配位位点，根据金属中心采用的配位数，形成了手性1D阶梯型网络和2D网格型结构。令人惊讶的是，对于2D网络，虽然CHCl 3溶剂分子的去除导致结构完整性的损失，但通过改变结晶条件和溶剂混合物仍然形成无溶剂晶体。
Two chiral porphyrin based ligands bearing, at their opposite meso positions, two appended pyridyl or ethynylpyridyl units and chiral groups have been designed. For each ligand, both enantiomers were synthesised. In the presence of the Zn(II) cation, the chiral ligands become self-complementary chiral metallatectons upon binding of the metal centre by the tetraaza core of the porphyrin. Owing to the presence of both free coordinating pyridyl units and Zn atoms offering one or two coordination sites within the same entity, depending on the coordination number adopted by the metal centre, chiral 1D stair type networks and 2D grid type architectures are formed. Surprisingly, for the 2D network, although the removal of CHCl3 solvent molecules leads to the loss of structural integrity, the solvent-free crystals are nevertheless formed by changing the crystallisation conditions and the solvent mixture.