Synthesis and Exciplex Emission of a Tricyano-substituted 9-Phenylfluorene Compound

Exciplex-emitters are attractive due to their distinct feature of easily achieving small singlet-triplet energy splitting for thermally activated delayed fluorescence(TADF),but face with challenges in convenient design of electron acceptors.New 9-phenylfluorene-based acceptor 9-[6-(2-cyano-7-isocyano-9-phenyl-9H-fluoren-9-yl)-9-ethyl-9H-carbazol-3-yl]-9-phenyl-9H-fluorene-2,7-dicarbonitrile(TriCNDPFCz)was designed and synthesized through tricyano-substitution.By mixing TriCNDPFCz with conventional donor 1,1-bis[(di-4-tolylamino)phenyl]cyclohexane(TAPC),bright exciplex-TADF was obtained with a maximum current efficiency of 46.7 cd·A^(-1),power efficiency of 52.3 lm·W^(-1)and external quantum efficiency of 14.5%.The experimental characterizations indicate that tricyano-substitution in 9-phenylfluorene skeleton can form strong electron-accepting ability,which is useful and convenient for constructing electron acceptor in exciplex emission.

A Cyano-Substituted Organoboron Electron-deficient Building Block for D-A Type Conjugated Polymers

The development of donor-acceptor(D-A)type conjugated polymers depends largely on the design of novel A building blocks.Herein,we report a novel A building block based on the cyano-substituted organoboron unit(SBN-3).Compared with the most common fluorine-substituted B←N unit,SBN-3 displays a significantly downshifted LUMO energy level because of the strong electron-withdrawing ability of cyano groups.In addition,due to the greater impact of cyano substitution on LUMO than on HOMO,SBN-3 exhibits a reduced band gap,nearinfrared absorption and fluorescence properties.The D-A type conjugated polymers based on the cyano-substituted B←N unit with thiophene-based units show narrow optical band gaps of ca.1.3 e V as well as distinctive electronic structures,i.e.,delocalized LUMOs and localized HOMOs.This work thus provides not only an effective approach to design strong A units but also a new electron-deficient building block for D-A type conjugated polymers.

Facile Fabrication of Aggregation-induced Emission Based Red Fluorescent Organic Nanoparticles for Cell Imaging

A cyano-substituted diarylethlene derivative aggregation-induced emission （ALE） dye with two amino end-groups and 4,4＇-（hexafluoroisopropylidene）diphthalic anhydride were facilely incorporated into red fluorescent organic nanoparticles （FONs） via room temperature anhydride ring-opening polymerization under an air atmosphere. These obtained RO-HFDA FONs were characterized by a series of techniques including gel permeation chromatography, Fourier transform infrared spectroscopy, size distribution and zeta potential measurements, UV-Vis absorption spectrum, fluorescent spectroscopy and transmission electron microscopy. Biocompatibility evaluation and cell uptake behavior of RO-HFDA FONs were further investigated to explore their potential biomedical application. We demonstrated that such FONs showed high water dispersibility, stable uniform spherical morphology （150-200 nm）, broad excitation band （350-605 nm）, intense red fluorescence （627 nm） and excellent biocompatibility, making them promising for cell imaging applications.

Photoredox/Ti dual-catalyzed dehydroxylative ring-opening Giese reaction of cyclobutanone oximes

A dehydroxylative ring-opening Giese reaction of cyclobutanone oximes enabled by photoredox/Ti dual catalysis has been reported in this work.This protocol avoids the prefunctionalization of oximes and the use of stoichiometric triarylphosphine reagents.It also features mild conditions,broad substrate scope and good functional group tolerance.The gram-scale reaction,product derivatization,late-stage functionalization of complex pharmaceutical and natural product derivatives,and oligopeptide modification exhibit the potential application of this methodology in synthetic chemistry.