Variable pore size, variable chemical functionality, and an example of reactivity within porous phenylacetylene silver salts
Variable pore size, variable chemical functionality, and an example of reactivity within porous phenylacetylene silver salts
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DOI：
10.1021/ja991100b
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发表时间：
1999-09-15
影响因子：
15
通讯作者：
Lobkovsky, EB
中科院分区：
文献类型：
--
作者：
Kiang, YH;Gardner, GB;Lobkovsky, EB
三氟甲磺酸银结晶的3重对称的1，3，5-三（4-乙炔基苯甲腈）苯的分子变体的研究揭示了几乎不变的假六方多孔结构类型。修饰涉及将侧基连接到母体分子的中心芳环。侧基包括乙烯基、芪、手性基团桃金娘烷醇和具有不同化学官能团的基团，如醇、醚和酯。修饰还包括在中心苯环和外围腈基之间添加延长的间隔单元。在这些分子中，1，3，5-三（4-乙炔基苯甲腈）苯的乙炔桥被二乙炔、乙炔基苯和二乙炔基苯型单元取代。对戊氧基-2，4，6-三（4-乙炔基苯甲腈）苯.AgOTf和1，3，5-三（4-（4-乙炔基苯甲腈）苯基）苯.AgOTf的单晶精修以及12个晶相的粉末数据显示了伪六边形通道的一致形成，表明母体多孔结构对于通道内部的功能修饰以及孔的扩大都是稳定的。戊氧基-2，4，6-三（4-乙炔基苯甲腈）苯。AgOTf在单斜空间群Am中精制。1，3，5-三（4-（4-乙炔基苯甲腈）苯基）苯，AgOTf为三斜晶系，空间群P（1），bar上。这些晶体具有直径分别为15埃和25埃的伪六方通道。基于粉末数据的晶胞常数与10至30埃范围内的通道直径相容。后者的通道直径是已知的有机多孔固体中最大的。引入手性桃金娘烷醇单元导致制备手性多孔固体。研究了这些相的热稳定性和化学稳定性。假六方结构被证明是稳定的，以完全从通道的溶剂损失。结果发现，在具有醇官能度的主体的情况下，酸酐客体，三氟乙酸酐，与主体反应形成酯，保留多孔结构类型。
Investigations on molecular variants of the 3-fold symmetric 1,3,5-tris(4-ethynylbenzonitrile)benzene crystallized with silver triflate revealed a nearly invariant pseudohexagonal porous structure type. Modifications involved the attachment of pendant groups to the central aromatic ring of the parent molecule. Pendant groups include the vinyl group, stilbene, the chiral group myrtanol, and groups with different chemical functionalities such as alcohols, ethers, and esters. Modifications also included the addition of elongated spacer units between the central benzene ring and the peripheral nitrile groups. In these molecules the acetylene bridges of 1,3,5-tris(4-ethynylbenzonitrile)benzene were replaced with diacetylene, ethynylbenzene, and diethynylbenzene type units. Single-crystal refinements for pentoxy-2,4,6-tris(4-ethynylbenzonitril)benzene.AgOTf and 1,3,5-tris(4-(4-ethynylbenzonitrile)phenyl)benzene.AgOTf as well as powder data on 12 crystalline phases showed the consistent formation of pseudohexagonal channels, demonstrating that the parent porous architecture is stable both to functional modification of the interior of the channel as well as to enlargement of the pores. Pentoxy-2,4,6-tris(4-ethynylbenzonitrile)benzene.AgOTf refined in the monoclinic space group Am. 1,3,5-Tris(4-(4-ethynylbenzonitrile)phenyl)benzene.AgOTf was found to be triclinic with space group P (1) over bar. These crystals have pseudohexagonal channels respectively 15 and 25 Angstrom in diameter. Cell constants based on powder data are compatible with channel diameters ranging from 10 to 30 Angstrom. The latter channel diameters are among the largest known for organic porous solids. The introduction of the chiral myrtanol unit led to the preparation of a chiral porous solid. The thermal and chemical stabilities of these phases were investigated. The pseudohexagonal structure proved stable to complete solvent loss from the channel. It was found in the case of a host with alcohol functionality that an acid anhydride guest, trifluoroacetic anhydride, reacted with the host to form an ester with retention of the porous structure type.