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β-Bis-CF3-substituted phosphorus corroles, theory and experiments
Inorganic Chemistry Frontiers ( IF 6.1 ) Pub Date : 2022-05-31 , DOI: 10.1039/d1qi01620b Xuan Zhan 1 , Zakir Ullah 2 , Donghyeon Kim 3 , Bilal Mustafa 2 , Hyungwook Kwon 2 , David G. Churchill 4, 5 , Zeev Gross 1
Inorganic Chemistry Frontiers ( IF 6.1 ) Pub Date : 2022-05-31 , DOI: 10.1039/d1qi01620b Xuan Zhan 1 , Zakir Ullah 2 , Donghyeon Kim 3 , Bilal Mustafa 2 , Hyungwook Kwon 2 , David G. Churchill 4, 5 , Zeev Gross 1
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16 bis-trifluoromethylated tpfc (5,10,15-tris(pentafluoro)corrole) phosphorus difluoride complexes were calculated; they were geometrically optimized and theoretically analyzed to help more completely understand the effect of multi-CF3 substitution in porphyrinoids. Six such compounds were experimentally prepared via two different reaction pathways: (i) treating the non-substituted (tpfc)PF2 and the mono-CF3-subsituted 1b, respectively, with FSO2CF2CO2Me and CuI yielded the previously reported compounds 1a–1d and the new bis-CF3 substituted complexes 2b–2e; and (ii) photoinduced generation of another bis-CF3 substituted species afforded 2f by using 1b as the starting material and dMeSCF3 as the CF3 source. The latter experimental pathway is, to the best of our knowledge, the first case of photocatalytic trifluoromethylation in porphyrin chemistry. Structural assignments of these newly prepared compounds were successfully achieved by the elaborate combination of experiments and calculations, which allowed compounds 2b–2f to be tentatively assigned as the Bis-2,3; Bis-2,17; Bis-3,13; Bis-7,12; and Bis-3,8 CF3-substituted corroles. Interestingly, the assignments were further supported by comparing experimental Rf values with calculated dipole moments of each isomer. Experimental UV-vis and fluorescence spectra, as well as cyclic voltammetry data obtained for 2a–2f allowed us to uncover clear differences of photophysical and electrochemical redox properties that were correlated with data from TDDFT energy level analyses.
中文翻译：
β-Bis-CF3-取代的磷化合物，理论与实验
计算了16个双三氟甲基化tpfc(5,10,15-三(五氟)咔咯)二氟化磷配合物；对它们进行了几何优化和理论分析，以帮助更全面地了解多CF 3取代在卟啉中的作用。通过两种不同的反应途径实验性地制备了六种此类化合物：(i)分别用 FSO 2 CF 2 CO 2 Me 和 CuI处理未取代的(tpfc)PF 2和单-CF 3取代的1b ，得到先前的报道了化合物1a-1d和新的 bis-CF 3取代的配合物2b-2e；(ii)通过使用1b作为起始材料和 dMeSCF 3作为 CF 3源，光诱导产生另一种双-CF 3取代物质，得到2f 。据我们所知，后一种实验途径是卟啉化学中光催化三氟甲基化的第一个案例。这些新制备的化合物的结构分配是通过实验和计算的精心组合成功实现的，这使得化合物2b-2f暂时被分配为Bis-2,3；双2,17；双3,13；双7,12；和Bis-3,8 CF 3 -取代的corroles。有趣的是，通过将实验R f值与计算的每个异构体的偶极矩进行比较，进一步支持了这些分配。实验 UV-vis 和荧光光谱，以及为2a-2f获得的循环伏安数据使我们能够发现与 TDDFT 能级分析数据相关的光物理和电化学氧化还原特性的明显差异。
更新日期：2022-05-31
中文翻译：
β-Bis-CF3-取代的磷化合物，理论与实验
计算了16个双三氟甲基化tpfc(5,10,15-三(五氟)咔咯)二氟化磷配合物；对它们进行了几何优化和理论分析，以帮助更全面地了解多CF 3取代在卟啉中的作用。通过两种不同的反应途径实验性地制备了六种此类化合物：(i)分别用 FSO 2 CF 2 CO 2 Me 和 CuI处理未取代的(tpfc)PF 2和单-CF 3取代的1b ，得到先前的报道了化合物1a-1d和新的 bis-CF 3取代的配合物2b-2e；(ii)通过使用1b作为起始材料和 dMeSCF 3作为 CF 3源，光诱导产生另一种双-CF 3取代物质，得到2f 。据我们所知，后一种实验途径是卟啉化学中光催化三氟甲基化的第一个案例。这些新制备的化合物的结构分配是通过实验和计算的精心组合成功实现的，这使得化合物2b-2f暂时被分配为Bis-2,3；双2,17；双3,13；双7,12；和Bis-3,8 CF 3 -取代的corroles。有趣的是，通过将实验R f值与计算的每个异构体的偶极矩进行比较，进一步支持了这些分配。实验 UV-vis 和荧光光谱，以及为2a-2f获得的循环伏安数据使我们能够发现与 TDDFT 能级分析数据相关的光物理和电化学氧化还原特性的明显差异。
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