An Alternate [2×2] Grid Constructed Around TiO 4 N 2 Units
An Alternate [2×2] Grid Constructed Around TiO 4 N 2 Units
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围绕 TiO 4 N 2 单元构建的替代 [2×2] 网格
DOI：
10.1002/chem.202200047
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Mobian, Pierre
中科院分区：
文献类型：
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作者：
Day, Erin;Kauffmann, Brice;Scarpi‐Luttenauer, Matthieu;Chaumont, Alain;Henry, Marc;Mobian, Pierre
报道了围绕TiO 4 N2基序构建的四核自组装物种的形成。该聚集体由Ti（OiPr）4、2，2 '-联嘧啶（bpym）和联苯酚链（L2 H4）产生，其中两个2，2'-联苯酚单元与联苯间隔基连接。[Ti4（L2）4（bpym）4]结构的固态结构揭示了前所未有的手性交替[2×2]网格的形成。除了[Ti 4（L2）4（bpym）4]架构的结构表征外，还使用DFT计算对各种可能的异构四聚体组装体（[2×2]网格、交替[2× 2]网格、圆形螺旋或环状半螺旋）进行几何优化。这些结果证实了交替的[2×2]网格比其他可能的四核异构体具有更高的稳定性，并且允许检查在四核组装体中由两种新的二亚胺螯合物（2，2 '-联吡啶=bipy和2，2'-联吡嗪= bipyz）替换bpym配体。从这个初步的理论研究，这三个氮配体之间的竞争在自组装过程中进行评估。总的来说，这项研究表明，交替的[2×2]网格的唯一形成是由CH N相互作用。
The formation of a tetranuclear self‐assembled species constructed around a TiO4N2motif is reported. This aggregate is generated from Ti(OiPr)4, 2,2’‐bipyrimidine (bpym) and a bis‐biphenol strand (L2H4) where two 2,2’‐biphenol units are connected with a biphenyl spacer. The solid‐state structure of the [Ti4(L2)4(bpym)4] architecture reveals the formation of an unprecedented chiral alternate [2×2] grid. In addition to the structural characterization of the [Ti4(L2)4(bpym)4] architecture, geometry optimisation on various possible isomeric tetrameric assemblies ([2×2] grid, alternate [2×2] grid, circular helicate or cyclic hemihelicate) is performed using DFT calculations. These results confirm the higher stability of the alternate [2×2] grid over the other possible tetranuclear isomers and allow examining the replacement of the bpym ligands by two novel diimine chelates within the tetranuclear assembly (2,2’‐bipyridine=bipy and 2,2’‐bipyrazine=bipyraz). From this initial theoretical investigation, the competition between these three nitrogen ligands in the course of the self‐assembly process is next evaluated. Overall, this investigation shows that the exclusive formation of the alternate [2×2] grid is driven by CH⋅⋅⋅N interactions.