Supramolecular Architectures of Pt(II) Complexes Controlled by Hydrogen Bonds and by Guest Molecules

The synthesis, the characterization, and the X-ray structures
of cis- and trans-Pt­(II) complexes
with α-(4-pyridyl)­benzhydrol
are reported. The crystal organization of several solvates is presented
and compared with particular regard to the role of the hydrogen bond
in the formation of the supramolecular architecture and how this is
regulated by the presence of guest solvent molecules. It is shown
that these networks are flexible as a response to the insertion of
small molecules. trans-Complexes reproduce the “venetian
blinds” pattern observed for the palladium analogs [Bacchi, A.; Bosetti, E.; Carcelli, M.; Pelagatti, P.; Rogolino, D.; Pelizzi, G. Inorg. Chem. 2005, 44, 431 and Bacchi, A.; Bosetti, E.; Carcelli, M. CrystEngComm 2005, 7, 527], while cis-complexes
persistently give supramolecular rectangles assisted by the concomitant
presence of OH···OH hydrogen bonds and edge-to-face
interactions between aromatic rings inside the rectangles. These rectangles
are packed by taking advantage of OH···Cl interactions
unless the guests provide other means of satisfying the hydrogen bond
donor/acceptor balance.

本报告阐述了cis-和trans-型Pt(II)与α-(4-吡啶基)苯甲醇配位化合物的合成、表征以及X射线晶体结构。其中，数种溶剂化合物的晶体结构组织被展示并相互比较，特别关注氢键在超分子结构形成中的作用及其如何受到客体溶剂分子的调控。研究表明，这些网络对小分子插入具有适应性。trans-型配合物重现了与钯类似物所观察到的“百叶窗”模式[Bacchi, A.; Bosetti, E.; Carcelli, M.; Pelagatti, P.; Rogolino, D.; Pelizzi, G. Inorg. Chem. 2005, 44, 431 和 Bacchi, A.; Bosetti, E.; Carcelli, M. CrystEngComm 2005, 7, 527]，而cis-型配合物则持续呈现由OH···OH氢键及矩形内部芳香环间的边面相互作用辅助的超分子矩形。这些矩形通过OH···Cl相互作用进行堆积，除非客体分子提供其他满足氢键供体/受体平衡的方法。