文献类型：期刊文献

英文题名：Longitudinal Extension of Double π-Helix Enables Near-Infrared Amplified Dissymmetry and Chiroptical Response

作者：Chen, Kai[1,2];Liu, Yujian[3];Wang, Zhaolong[4,5];Hu, Shunlong[1,2];Zhao, Yilun[1,2];Wang, Wei[1,2];Liu, Guogang[1,2];Wang, Zhaohui[1,2,3];Jiang, Wei[3]

机构：[1]East China Univ Sci & Technol, Sch Chem & Mol Engn, Feringa Nobel Prize Scientist Joint Res Ctr, Inst Fine Chem,Frontiers Sci Ctr Materiobiol & Dyn, Shanghai 200237, Peoples R China;[2]East China Univ Sci & Technol, Sch Chem & Mol Engn, Feringa Nobel Prize Scientist Joint Res Ctr, Joint Int Res Lab Precis Chem & Mol Engn,Inst Fine, Shanghai 200237, Peoples R China;[3]Tsinghua Univ, Dept Chem, Key Lab Organ Optoelect & Mol Engn, Beijing, Peoples R China;[4]Chinese Acad Sci, Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China;[5]Chinese Acad Sci, Dalian Inst Chem Phys, Collaborat Innovat Ctr Chem Energy Mat iChEM, Dalian 116023, Peoples R China

年份：2024

卷号：146

期号：19

起止页码：13499

外文期刊名：JOURNAL OF THE AMERICAN CHEMICAL SOCIETY

收录：;EI(收录号：20241916054355);WOS:【SCI-EXPANDED(收录号:WOS:001225405200001)】；

基金：This work was financially supported by the National Natural Science Foundation of China (NSFC) (No. 22122503, 22235005, and 22275112).

语种：英文

外文关键词：Bioimaging - Circular polarization - Density functional theory - Dichroism - Infrared devices - Naphthalene

摘要：Near-infrared (NIR) circularly polarized light absorbing or emitting holds great promise for highly sensitive and precise bioimaging, biosensing, and photodetectors. Aiming at designing NIR chiral molecular systems with amplified dissymmetry and robust chiroptical response, herein, we present a series of double pi-helical dimers with longitudinally extended pi-entwined substructures via Ullmann or Yamamoto homocoupling reactions. Circular dichroism (CD) spectra revealed an approximate linear bathochromic shift with the rising number of naphthalene subunits, indicating a red to NIR chiroptical response. Particularly, the terrylene diimide-entwined dimers exhibited the strongest CD intensities, with the maximal |Delta epsilon| reaching up to 393 M-1 cm(-1) at 666 nm for th-TDI[2]; and a record-high chiroptical response (|Delta Delta epsilon|) between the neutral and dianionic species of 520 M-1 cm(-1) at 833 nm for th-TDI[2]Cl was achieved upon further reduction to its dianionic state. Time-dependent density functional theory (TDDFT) calculations suggested that the pronounced intensification of the CD spectra originated from a simultaneous enhancement of both electric (mu) and magnetic (m) transition dipole moments, ultimately leading to an overall increase in the rotatory strength (R). Notably, the circularly polarized luminescence (CPL) brightness (B-CPL) reached 77 M-1 cm(-1) for th-TDI[2]Cl, among the highest values reported for NIR-CPL emitters. Furthermore, all chiral dianions exhibited excellent air stability under ambient conditions with half-life times of up to 10 days in N-methylpyrrolidone (NMP), which is significant for future biological applications and chiroptic switches.