Combined Experimental and Theoretical Studies on Planar Chirality of Partially Overlapped C2-Symmetric [3.3](3,9)Dicarbazolophanes
Combined Experimental and Theoretical Studies on Planar Chirality of Partially Overlapped C2-Symmetric [3.3](3,9)Dicarbazolophanes
复制标题
部分重叠C2对称平面手性的实验与理论联合研究[3.3](3,9)二咔唑啉
DOI：
10.1021/acs.jpca.0c00286
复制
发表时间：
2020
期刊：
影响因子：
--
通讯作者：
Mori Tadashi
中科院分区：
文献类型：
--
作者：
Tani Keita;Imafuku Risa;Miyanaga Kanae;Masaki Miyuki Eiraku;Kato Haruka;Hori Kazushige;Kubono Koji;Taneda Masatsugu;Harada Takunori;Goto Kenta;Tani Fumito;Mori Tadashi
部分重叠的二氨基甲苯表现出平面手性。本研究首次用制备手性高效液相色谱拆分了C2对称的[3.3](3，9)二氨基甲苯衍生物(CZ1-CZ3)。在它们的圆二向色性(CD)谱中，它们的1L带1晶格(|Δε|=10~(-12)和51~57M~(-1)cm~(-1))有中等的Cotton效应(CES)，而它们的1B跃迁(|Δε|=156~216M~(-1)cm~(-1))有很强的Ces，吸收不对称性(GABS)因子在10~(-2)数量级。氰胺类化合物CZ1也得到了圆偏振发光谱，其相对发光不对称性(GLUM)因子为0.013。计算研究被用来解决这些平面手性的二卡巴唑环中如此显著的手性反应的因素。通过实验和理论CD光谱的比较，明确地确定了绝对构型，这一点得到了对映体纯磺酰胺衍生物CZ2的X-射线晶体结构分析的证实。
Partially overlapped dicarbazolophanes exhibit a planar chirality. In this study,C2-symmetrical [3.3](3,9)dicarbazolophane derivatives (CZ1–CZ3) have been optically resolved by preparative chiral high-performance liquid chromatography for the first time. In their circular dichroism (CD) spectra, moderate Cotton effects (CEs) were observed for their1Lband1Latransitions (|Δε| = 10–12 and 51–57 M–1cm–1, respectively), while intense CEs were notified in their1B transitions (|Δε| = 156–216 M–1cm–1), absorption dissymmetry (gabs) factors being in orders of 10–2. Circularly polarized luminescence spectrum was also obtained for cyanamide derivativeCZ1, with a comparative luminescence dissymmetry (glum) factor of 0.013. A computational investigation was applied to address the factors for such remarkable chiroptical responses in these dicarbazolophanes of planar chirality. Absolute configurations were unambiguously determined by the comparison of experimental and theoretical CD spectra, which was affirmed by the X-ray crystal structural analysis of enantiomerically pure sulfonamide derivativeCZ2.