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Self-assembly of silver(I) and ditopic heteroscorpionate ligands. Spontaneous chiral resolution in helices and sequence isomerism in coordination polymers

机译:银(I)和异位异蝎配体的自组装。螺旋中的自发手性拆分和配位聚合物中的序列异构

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摘要

The self-assembly of the ligands bis(pyrazol-1-yl)(pyridine-4-yl)methane (L~1) and bis(3,5-dimethylpyrazol-1-yl)(pyridine-4-yl)methane (L ~2) with AgBF_4 leads to three types of species: L ~1 gives rise to the formation of a boxlike cyclic dimer (1) while L~2 leads to two different coordination polymers that are sequence isomers. With dependence on the crystallization conditions, either a homochiral helix (2) with spontaneous resolution or a zigzag polymer is formed (3). By means of solid-state circular dichroism studies, the presence of both enantiomers in 2 is observed, enriched locally in colonies of crystals. The homochiral motif is stable, even upon removal of guest solvent molecules. The noncovalent interactions in the crystalline structure are clearly affected by the presence of the methyl groups on the pyrazolyl rings. The behavior of the compounds in solution is discussed.
机译:配体双(吡唑-1-基)(吡啶-4-基)甲烷(L〜1)和双(3,5-二甲基吡唑-1-基)(吡啶-4-基)甲烷(具有AgBF_4的L〜2导致三种类型的物质:L〜1导致形成盒状环状二聚体(1),而L〜2导致两种不同的配位聚合物,它们是序列异构体。取决于结晶条件,形成具有自发拆分的同手性螺旋(2)或之字形聚合物(3)。通过固态圆二色性研究,观察到两种对映异构体均以2存在,在晶体菌落中局部富集。即使除去客体溶剂分子,同手性基序也是稳定的。吡唑基环上甲基的存在明显影响晶体结构中的非共价相互作用。讨论了化合物在溶液中的行为。

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