Mądry Tomasz, Czapik Agnieszka, Kwit Marcin
Department of Chemistry, Adam Mickiewicz University, Umultowska 89B, 61 614 Poznan, Poland.
Center for Advanced Technologies, Adam Mickiewicz University, Umultowska 89C, 61 614 Poznan, Poland.
ACS Omega. 2019 Feb 14;4(2):3244-3256. doi: 10.1021/acsomega.8b03337. eCollection 2019 Feb 28.
Chirality transfer from circular dichroism (CD)-silent secondary alcohol (inductor) to the stereodynamic bichromophoric di(1-naphthyl)methane probe (reporter) led to the generation of intense, induced exciton-type Cotton effects (CEs) in the ultraviolet-visible absorption region. The di(1-naphthyl)methane probe exhibits extraordinarily high sensitivity to even small structural variations of the alcohol skeleton, that is, the probe is able to distinguish between an oxygen atom and a methylene group in a 3-hydroxytetrahydrofurane skeleton. Signs and amplitudes of the exciton couplets of B electronic transition might be correlated with the type of stereo-differentiating parts of the molecule flanking the stereogenic center, however, not with the absolute configuration. The origin of the induced CEs was established by means of experimental and theoretical methods. As a result, a mechanism of chirality transfer from the permanent stereogenic center to the bichromophore is proposed.
手性从圆二色性（CD）沉默的仲醇（诱导剂）转移至立体动力学双发色团二（1-萘基）甲烷探针（报告基团），导致在紫外-可见吸收区域产生强烈的、诱导激子型的科顿效应（CEs）。二（1-萘基）甲烷探针对于醇骨架的哪怕很小的结构变化都表现出极高的灵敏度，也就是说，该探针能够区分3-羟基四氢呋喃骨架中的氧原子和亚甲基。B电子跃迁的激子偶合的符号和振幅可能与手性中心两侧分子的立体区分部分的类型相关，然而，与绝对构型无关。通过实验和理论方法确定了诱导CEs的起源。结果，提出了一种从永久手性中心到手性双发色团的手性转移机制。
