Luminescent polymers are generally constructed through polymerization of luminescent moieties. Polymerization itself, however, is mainly used for constructing polymer main chain, and the importance of polymerization on luminescence has yet to be explored. Here, we demonstrate a polymerization-induced emission strategy producing luminescent polymers by introducing Barbier reaction to hyperbranching polymerization, which allows luminescent properties to be easily tuned from the traditional type to an aggregation-induced emission type by simply adjusting the monomer structure and the polymerization time. When rotation about the phenyl groups in hyperbranched polytriphenylmethanols (HPTPMs) is hindered, HPTPMs exhibit traditional emission property. When all phenyl groups of HPTPM are rotatable, i.e., p,p′,p″-HPTPM, it exhibits interesting aggregation-induced emission property with tunable emission colors from blue to yellow, by just adjusting polymerization time. Further applications of aggregation-induced emission type luminescent polymers are illustrated by the facile fabrication of white light-emitting diode (LED) and light-harvesting film with an antenna effect >14. This Barbier hyperbranching polymerization-induced emission provides a new strategy for the design of luminescent polymers and expands the methodology and functionality library of both hyperbranching polymerization and luminescent polymers.

Many reactions involving allenyl ion species have been studied, but reactions involving allenyl radicals are less well understood, perhaps because of the inconvenience associated with the generation of short-lived allenyl radicals. We describe here a versatile method for the generation of allenyl radicals and their previously unreported applications in the intermolecular 1,4-carbocyanation and 1,4-sulfimidocyanation of 1,3-enynes. With the assistance of the trifunctional reagents, alkyl diacyl peroxides or N-fluorobenzenesulfonimide, a range of synthetically challenging multisubstituted allenes can be prepared with high regioselectivity. These multisubstituted allenes can be easily transformed into synthetically useful structures such as fluorinated vinyl cyanides, lactones, functionalized allenyl amides, 1-aminonaphthalenes, and pyridin-2­(1H)-ones, and several novel transformations are reported. The results of radical scavenger and radical clock experiments are consistent with the proposed allenyl radical pathway. Density functional theory (DFT) and IR spectroscopy studies suggest the formation of an isocyanocopper­(II) species in the ligand exchange step. On the basis of the results of IR, DFT, and diastereoselectivity studies, an isocyanocopper­(II)/copper­(I) catalytic cycle is proposed, which differs from the previously considered Cu­(III) mechanism in cyanation reactions.

As imple and efficient synthesis of NBN-doped conjugated polycyclic aromatic hydrocarbons (sucha sd iazaborinines) has been accomplished by ac atalyst-free intermolecular dehydration reaction at room temperature between boronic acid and diamine moieties with yields up to 99 %. Polycyclic aromatic hydrocarbons with as ix-membered NBN ring are an ew class of aggregation-induced emissive luminogens.E xtremely sensitive detection of ppb levels of TNT by phenyl naphthodiazaborinine is straightforward. Visual detection of TNT is illustrated by fabrication of TNT test strips, which can detect as little as 100 ng of TNT powder.This simple and sensitive detection of TNT has potential applications in the area of public safety and security against terrorist activities.Doping of polycyclica romatic hydrocarbons (PAHs) with boron-nitrogen units,t hat is,i soelectronic and isosteric replacement of aC =Cb ond with aB ÀNb ond (Scheme 1), has emerged as av ersatile strategy for the preparation of novel hybrid PA Hs with unusual and attractive optical, electronic,a nd chemical properties that are absent from their C=Cc ongeners. [1] Them olecular design of boronnitrogen-doped PA Hs therefore expands the structure and functionality library of p-systems,and such chemistry is highly desirable in the development of useful materials. [2] For example,since the pioneering work on BN doped p-systems, namely azaborinines,b yD ewar and White in the 1960s, considerable research effort has been devoted by,for example Ashe,L iu, Braunschweig,S chäfer,a nd Jäkle [3] to the synthesis,p roperties,a nd reactivity of azaborinines.S ince Weberspioneering work on NBN-doped compounds,specifically diazaborinines,t here have been numerous investigations of their synthesis,o na ccount of their potential applications as drugs and as reagents that can be used in the Suzuki-Mayaura reaction. [4] Although considerable progress has been made in boron-nitrogen doped p-systems,t he currently available preparative methods suffer from the need for rigorous reaction conditions including the requirement for conditions which are air-and/or moisture-free,multiple steps and unsatisfactory total yield. Finding as imple and mild strategy with which to synthesize boron-nitrogen-doped PA Hs is therefore significant and highly desirable.Boron-containing p-systems have attracted considerable research attention since the 1960s due to their desirable optical, electronic, and sensory properties. [5] With the presence of an empty porbital of the boron center in p-systems, such compounds are luminogens and are widely utilized as such. [6] Tr aditional luminogens fluoresce strongly in dilute solution but are subject to aggregation-caused quenching (ACQ) [7] and the luminogens are quenched at higher concentrations or in aggregation states.I n2 001, Tang described the aggregation-induced emission (AIE) of luminogens (AIEgens), [8] which fluoresce weakly when dissolved, but emit strongly when aggregated. As an important class of luminogens,b oron containing p-systems featuring AIE,...

No abstract