Bauzá Antonio, Frontera Antonio
Department of Chemistry Universitat de les Illes Balears, Crta. de Valldemossa km 7.5, 07122 Palma (Baleares), Spain.
Phys Chem Chem Phys. 2016 Jul 27;18(30):20381-8. doi: 10.1039/c6cp03862j.
In this manuscript the ability of hydrogen and halogen bonding interactions, as well as metal coordination to enhance FF interactions involving fluorine substituted aromatic rings has been studied at the RI-MP2/def2-TZVPD level of theory. We have used 4-fluoropyridine, 4-fluorobenzonitrile, 3-(4-fluorophenyl)propiolonitrile and their respective meta derivatives as aromatic compounds. In addition, we have used HF and IF as hydrogen and halogen bond donors, respectively, and Ag(i) as the coordination metal. Furthermore, we have also used HF as an electron rich fluorine donor entity, thus establishing FF interactions with the above mentioned aromatic systems. Moreover, a CSD (Cambridge Structural Database) search has been carried out and some interesting examples have been found, highlighting the impact of FF interactions involving aromatic fluorine atoms in solid state chemistry. Finally, cooperativity effects between FF interactions and both hydrogen and halogen bonding interactions have been analyzed and compared. We have also used Bader's theory of "atoms in molecules" to further describe the cooperative effects.
在本论文中，我们在RI-MP2/def2-TZVPD理论水平下研究了氢键、卤键相互作用以及金属配位作用增强涉及氟取代芳香环的氟-氟相互作用（FF相互作用）的能力。我们使用了4-氟吡啶、4-氟苯腈、3-(4-氟苯基)丙炔腈及其各自的间位衍生物作为芳香族化合物。此外，我们分别使用HF和IF作为氢键和卤键供体，并使用Ag(i)作为配位金属。此外，我们还使用HF作为富电子氟供体实体，从而与上述芳香族体系建立FF相互作用。此外，我们还进行了剑桥晶体结构数据库（CSD）搜索，并发现了一些有趣的例子，突出了涉及芳香氟原子的FF相互作用在固态化学中的影响。最后，我们分析并比较了FF相互作用与氢键和卤键相互作用之间的协同效应。我们还使用了Bader的“分子中的原子”理论来进一步描述协同效应。
