Waters Jessica E, Berger Georg, Peel Andrew J, García-Rodríguez Raúl, Bond Andrew D, Wright Dominic S
Yusuf Hamied Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge, CB2 1EW, UK.
Anorganisch-Chemisches Institut, Heidelberg University, Im Neuenheimer Feld 270, 69120, Heidelberg, Germany.
Chemistry. 2021 Aug 19;27(47):12036-12040. doi: 10.1002/chem.202101291. Epub 2021 Jun 28.
Supramolecular main group chemistry is a developing field which parallels the conventional domain of metallo-organic chemistry. Little explored building blocks in this area are main group metal-based ligands which have the appropriate donor symmetry to build desired molecular or extended arrangements. Tris(pyridyl) main group ligands (E(py) , E=main group metal) are potentially highly versatile building blocks since shifting the N-donor arms from the 2- to the 3-positions and 4-positions provides a very simple way of changing the ligand character from mononuclear/chelating to multidentate/metal-bridging. Here, the coordination behaviour of the first main group metal tris(4-pyridyl) ligands, E(4-py) (E=Sb, Bi, Ph-Sn) is explored, as well as their ability to build metal-organic frameworks (MOFs). The complicated topology of these MOFs shows a marked influence on the counter anion and on the ability of the E(4-py) ligands to switch coordination mode, depending on the steric and donor character of the bridgehead. This structure-directing influence of the bridgehead provides a potential building strategy for future molecular and MOF design in this area.
超分子主族化学是一个与传统金属有机化学领域并行发展的领域。该领域中尚未充分探索的构建单元是具有合适供体对称性以构建所需分子或扩展结构的主族金属基配体。三（吡啶基）主族配体（E(py) ，E = 主族金属）可能是极具通用性的构建单元，因为将氮供体臂从2-位转移到3-位和4-位提供了一种非常简单的方法来改变配体性质，从单核/螯合变为多齿/金属桥连。在此，研究了首个主族金属三（4-吡啶基）配体E(4-py) （E = Sb、Bi、Ph-Sn）的配位行为，以及它们构建金属有机框架（MOF）的能力。这些MOF复杂的拓扑结构对抗衡阴离子以及E(4-py) 配体切换配位模式的能力显示出显著影响，这取决于桥头的空间位阻和供体性质。桥头的这种结构导向影响为该领域未来的分子和MOF设计提供了一种潜在的构建策略。
