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Bowl-shaped polyaromatic hydrocarbons (buckybowls): Crystal packing and metal binding reactions.

机译：碗形的聚芳烃（buckybowls）：晶体堆积和金属结合反应。

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This work is a part of a broad program in our laboratory dedicated to the investigation of a new class of non-planar polyaromatic hydrocarbons that map onto the surfaces of fullerenes (and referred to as buckybowls). It focuses on the preparation of buckybowls, their molecular and solid state structures, and reactivity in metal binding reactions. For the first time, the structures of all available buckybowls have been analyzed using X-ray diffraction data collected in the course of this work, as well as data previously obtained in our group or reported by others (and dearchived from the Cambridge Structural Database). Forces governing the packing arrangements of nonplanar polyaromatic surfaces into three-dimensional solid-state networks have been discussed. Furthermore, the reactivity of bowl-shaped polyarenes toward coordinatively unsaturated electrophilic dirhodium(II) and trimercury(II) complexes have been tested. Bromocorannulene and monoindenocorannulene were selected to react with the volatile dirhodium(II) tetratrifluoroacetate complex in a solvent-free environment. Several new products were isolated and fully characterized, including the first complex in which rhodium(II) centers coordinate to the interior part of a p-bowl. To probe the interactions between planar and non-planar surfaces, a planar trimercury(II) complex was chosen to react with a number of bowl-shaped polyarenes. In the solid state, the interacting moieties form binary stacks of alternating planar and non-planar surfaces and exhibit a very strong mutual effect on each other. Thus, one can tune the amount of strain energy imposed at the molecular level by using non-planar polyarenes as templates for bending planar metal complexes. The extent of this effect is discussed in detail.
机译：这项工作是我们实验室中一项广泛计划的一部分，该计划致力于研究映射到富勒烯（并称为buckybowls）表面上的一类新的非平面聚芳烃。它专注于buckybowls的制备，它们的分子和固态结构以及在金属结合反应中的反应性。首次使用这项工作过程中收集的X射线衍射数据以及先前在我们小组中获得的数据或其他人的报告（并从Cambridge Structural Database解存档）对所有可用的buckybowl的结构进行了分析。 。已经讨论了控制非平面多芳族表面进入三维固态网络的排列方式的力。此外，已经测试了碗形聚芳烃对配位不饱和的亲电dirhodium（II）和trimercury（II）配合物的反应性。选择溴化环戊二烯和单茚并环戊二烯在无溶剂的环境中与挥发性四氢三氟乙酸二钠（II）反应。分离出了几种新产品并对其进行了充分表征，包括第一个复合物，其中铑（II）的中心与p形碗的内部协调。为了探测平面和非平面表面之间的相互作用，选择了平面三聚氰胺（II）配合物与许多碗形聚芳烃反应。在固态下，相互作用的部分形成交替的平面和非平面表面的二元堆叠，并且彼此展现出非常强的互作用。因此，通过使用非平面聚芳烃作为弯曲平面金属络合物的模板，可以调节在分子水平施加的应变能的数量。详细讨论了这种影响的程度。

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