A new bridging chelating ligand for crystal engineering: Synthesis, polymorphism, and two modes of assembly of 1,4-bis(3-phenyl-1,3-propanedion)benzene with metal cations resulting in either discrete or polymeric complexes
A new bridging chelating ligand for crystal engineering: Synthesis, polymorphism, and two modes of assembly of 1,4-bis(3-phenyl-1,3-propanedion)benzene with metal cations resulting in either discrete or polymeric complexes
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DOI：
10.1021/cg030016b
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发表时间：
2003-11-01
影响因子：
3.8
通讯作者：
Ripmeester, JA
中科院分区：
文献类型：
--
作者：
Soldatov, DV;Zanina, AS;Ripmeester, JA
本工作引入了一种新的配体(H_2L，PhCOCH2COPhCOCH2COPh)，它具有两个由苯环隔开的β-二酮基团。以两种不同的修饰方式合成并分离了游离基。该配体倾向于两种基本构象类型中的一种，其中β-二酮基团近似共面，或者定向在相对的一侧(反式)，或者在彼此接近60度的同一侧(顺式)。在自由状态下，配体以100%的烯醇形式存在；在固体状态下，它采用反式构象。在一维(一维)配位聚合物[ZnPy2L](N)*NPY中，配体采用反式构象，并与两个锌(II)中心络合，桥连在11.3埃。在所研究的三个晶体中，观察到了另一种结构，其理想式为[M3Py6L3]*5(CHCl3)。在这种情况下，配体采用顺式构象，并在10.7埃处与连接它们的两个金属中心螯合，生成三核大环物种。在晶体中，这些三角形堆积在一起，形成了容纳氯仿作为客体的通道。所研究的特定晶体的总组成如下：[Co3Py6L3]*4.84(CHCl3)、[Co3Py6L3]*4.11(CHCl3)和[Ni3Py6L3]*4.68(CHCl3)。该体系结构表现出灵活性和沸石样的行为。
This work introduces a new ligand (H2L, PhCOCH2COPhCOCH2COPh) bearing two beta-diketonate functions separated by a phenylene ring. The free ligand was synthesized and isolated in two polymorphic modifications. The ligand exhibits a preference for one of two basic conformational types where beta-diketonate functions are approximately coplanar and directed either on opposite sides (trans) or on the same side similar to60degrees to each other (cis). In the free form, the ligand exists as 100% enol; in the solid state, it adopts a trans conformation. In a one-dimensional (1D) coordination polymer [ZnPy2L](n)*nPy, the ligand adopts the trans conformation and chelates to two zinc(II) centers bridging them at 11.3 Angstrom. In three of the crystals studied, another structure was observed with an ideal formula [M3Py6L3]*5(CHCl3). In this case, the ligand adopts a cis conformation and chelates to two metal centers bridging them at 10.7 Angstrom, to produce a trinuclear macrocyclic species. In the crystal, these triangles pack to create channels that accommodate chloroform as a guest. The specific crystals studied had the following overall Compositions: [Co3Py6L3]*4.84(CHCl3), [Co3Py6L3]*4.11(CHCl3), and [Ni3Py6L3]*4.68(CHCl3). The architecture displays flexibility and zeolite-like behavior.