Corrigendum: Physicochemical and Electronic Properties of Cationic [6]Helicenes: from Chemical and Electrochemical Stabilities to Far-Red (Polarized) Luminescence.
Corrigendum: Physicochemical and Electronic Properties of Cationic [6]Helicenes: from Chemical and Electrochemical Stabilities to Far-Red (Polarized) Luminescence.
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勘误表：阳离子[6]螺旋烯的物理化学和电子性质：从化学和电化学稳定性到远红（偏振）发光。
DOI：
10.1002/chem.201901658
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发表时间：
2019
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作者：
Bosson,Johann;Labrador,GeraldineM;Pascal,Simon;Miannay,François-Alexandre;Yushchenko,Oleksandr;Li,Haidong;Bouffier,Laurent;Sojic,Neso;Tovar,RobertoC;Muller,Gilles;Jacquemin,Denis;Laurent,AdèleD;LeGuennic,Boris;Vauthey,Eric;
阳离子二氧杂合物1、氮杂合物2和氮杂合物3[6]螺旋烯的理化性质表明，与氮杂合物2 （pKR+ 15.2，𝐸1/2𝑟𝑒𝑑-0.45 V）和二氧杂合物1 （pKR+ 8.8，𝐸1/2𝑟𝑒𝑑-0.12 V）类似物相比，氮杂合物3 （pKR+ 20.4，𝐸1/2𝑟𝑒𝑑-0.72 V）具有更高的化学稳定性。建立了这些阳离子发色团的荧光，荧光范围从橙色到远红色。从1到3，观察到最低能量跃迁（在乙腈中高达614 nm）的色移和荧光量子产率和寿命的增强（在658 nm处高达31%和9.8 ns）。本文还报道了三态量子产率和圆偏振发光。最后，通过选择性和正交的后官能化反应（12个例子，化合物4-15）实现了双氮[6]螺旋核光学性质的微调。电子吸收调制从橙色到远红色光谱范围（560-731 nm），而荧光从591到755 nm，增强量子效率高达70%（619 nm）。通过第一性原理计算证明了外围氧化色素取代基的影响。
Physicochemical properties of cationic dioxa 1, azaoxa 2 and diaza 3 [6] helicenes demonstrate a much higher chemical stability of diaza adduct 3 (pKR+ 20.4, 𝐸1/2 𝑟𝑒𝑑‒0.72 V) compared to azaoxa 2 (pKR+ 15.2, 𝐸1/2 𝑟𝑒𝑑‒0.45 V) and dioxa 1 (pKR+ 8.8, 𝐸1/2 𝑟𝑒𝑑‒0.12 V) analogues. The fluorescence of these cationic chromophores was established and ranges from the orange to the far-red regions. From 1 to 3, a bathochromic shift of the lowest energy transitions (up to 614 nm in acetonitrile) and an enhancement of the fluorescence quantum yields and lifetimes (up to 31% and 9.8 ns at 658 nm) are observed. The triplet quantum yields and the circularly polarized luminescence are also reported. Finally, fine tuning of the optical properties of the diaza [6] helicene core was achieved through selective and orthogonal post-functionalization reactions (12 examples, compounds 4-15). The electronic absorption is modulated from the orange to far-red spectral range (560-731 nm) while fluorescence is observed from 591 to 755 nm with enhanced quantum efficiency up to 70%(619 nm). The influence of the peripheral auxochrome substituents is rationalized by first-principles calculations.