Perfluorinated and Half-Fluorinated Rubrenes: Synthesis and Crystal Packing Arrangements
Perfluorinated and Half-Fluorinated Rubrenes: Synthesis and Crystal Packing Arrangements
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DOI：
10.1021/acs.joc.7b01383
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发表时间：
2017-08-04
影响因子：
3.6
通讯作者：
Suzuki, Toshiyasu
中科院分区：
文献类型：
--
作者：
Sakamoto, Youichi;Suzuki, Toshiyasu
采用全氟1,3-二苯基异苯并呋喃和1,4-二苯基-2,3-二脱氢萘经还原脱氧合成全氟脲（PF-RUB）。该方法易于用于半氟化rubrene （F-14-RUB）的合成。电化学测量和DFT计算表明，全氟化强烈降低HOMO和LUMO能量。PF-RUB的再结晶和升华分别得到两种不同的平面和扭曲构象晶体。在这两种情况下，全氟化导致短C-F和F-F接触的形成，并完全破坏面对面的pi相互作用。通过升华法制备了F-14-RUB单晶，扭曲分子在3.54埃的面对面距离上呈现出二维pi堆叠。
Perfluororubrene (PF-RUB) has been synthesized by cydoaddition of perfluorinated 1,3-diphenylisobenzofuran and 1,4-diphenyl-2,3-didehydronaphthalene followed by reductive deoxygenation. This method was easily applied for the synthesis of half-fluorinated rubrene (F-14-RUB). The electrochemical measurements and DFT calculations indicate that perfluorination strongly lowers the HOMO and LUMO energies. Recrystallization and sublimation of PF-RUB gave two different crystals with planar and twisted conformations, respectively. In both cases, perfluorination leads to the formation of short C-F and F-F contacts and completely disrupts face-to-face pi interactions. Single crystals of F-14-RUB were grown by sublimation, and twisted molecules display the two-dimensional pi-stacking with a face-to-face distance of 3.54 angstrom.