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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Bowl shaped deformation in a planar aromatic polycycle upon reduction. Li and Na separated dianions of the aromatic polycycle 5,6:11,12-di-o-phenylene-tetracene
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Bowl shaped deformation in a planar aromatic polycycle upon reduction. Li and Na separated dianions of the aromatic polycycle 5,6:11,12-di-o-phenylene-tetracene

机译：减少时，在平面芳族多卷中的碗形变形。 李和Na分离的芳族多卷曲的圆锥5,6：11,12-Di-O-苯基 - 四烯

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摘要

Herein we report the synthesis and crystal structures of three light alkali metal salts of the dianion of the polycyclic aromatic hydrocarbon 5,6:11,12-di-o-phenylenetetracene (L-DOPT). The compounds are obtained by reaction of L-DOPT with an excess of lithium or sodium metal in different O-donor solvents (DME, diglyme) and crystallize as naked, solvated-cation separated dianions exhibiting no interaction between the alkali metal ion and the aromatic pi-system of L-DOPT. Depending on the aprotic etheral solvent and the hardness of the alkaline metal agent a significant structural perturbation of the conjugated carbon framework of L-DOPT is observed resulting in a bowl shaped curvature of the anionic pi-perimeter, in contrast to its fully planar neutral state. Reduction of L-DOPT with lithium in DME results in the formation of the solvent-separated molecular structure of {[(DME-kappa O-2)(3)Li+](2)(L-DOPT(2-))}(2) 1 containing naked isolated units of dianionic L-DOPT. A similar structural arrangement is observed for the corresponding sodium compound {[(DME-kappa O-2)(3)Na+](2)(L-DOPT(2-))}(2) 2 in which, however, a lesser curvature of the isolated dianionic ligand skeleton compared to 1 is observed. In contrast to 1 and 2 reduction with sodium in diglyme results in the formation of {[(diglyme-kappa O-3)(2)Na+](2)(L-DOPT(2-))}(0.5) 3. The deformation of the peripheric phenylene rings of [L-DOPT(2-)] in 3 is not as pronounced as compared to 1 and 2. Nevertheless, molecular structures of 1-3 deviate from full-planarity as observed in the parent neutral LDOPT. No preferential endo- or exo-site coordination of the alkaline metal cations Li+ and Na+ on the curved dianionic pi-perimeter is observed.
机译：在此，我们报告了多环芳烃5,6：11,12-Di-O-苯基乙烯（L-DOPT）的脱膜的三个光碱金属盐的合成和晶体结构。通过L-DOPT在不同O-供体溶剂（DME，DIGLYME）中的过量的锂或钠金属的反应得到的化合物获得，并将溶剂化阳离子分离的圆锥在碱金属离子和芳族之间的相互作用中结晶。 L-DOPT的PI系统。取决于非质子醚溶剂和碱金属剂的硬度，观察到L-DOPT的共轭碳框架的显着结构扰动，导致阴离子Pi-周边的碗形曲率，与其完全平坦的中立状态相反。 DME中锂的L-DOPT的降低导致形成溶剂分离的分子结构的{[（DME-Kappa O-2）（3）Li +]（2）（L-DOPT（2 - ））}（ 2）1包含Dianionic L-Dopt的裸体分离单位。对相应的钠化合物（DME-Kappa O-2）（3）Na +]（2）（L-DOPT（2 - ））}（2）2，观察到类似的结构布置，然而分离的Dianionic配体骨架的曲率与1相比。与1和2中的1和2含量在Diglyme中导致{[（Diglyme-Kappa O-3）（2）Na +]（2）（L-DOPT（2 - ））}（0.5）3。 [L-DOPT（2-）]在3中的周边亚苯并环的变形并不像1和2.相比的那样明显。然而，1-3的分子结构偏离母体中性LDOPT中观察到的全平面性。观察到碱性金属阳离子Li +和Na +的优先内部或外部位点在弯曲的Dianionic Pi-urimer上的Na +的配位。

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