Clickable Polymerization-Induced Emission Luminogens Toward Color-Tunable Modification of Non-Traditional Intrinsic Luminescent Polymers.

Non-traditional intrinsic luminescent (NTIL) polymer is an emerging field, and its color-tunable modification is highly desirable but still rarely investigated. Here, a click chemistry approach for the color-tunable modifications of NTIL polymers by introducing clickable polymerization-induced emission luminogen (PIEgen), is demonstrated. Through Cu-catalyzed azide-alkyne cycloaddition click chemistry, a series of PIEgens is successful prepared, which is further polymerized via reversible addition-fragmentation chain transfer (RAFT) polymerization. Interestingly, after clickable modification, these monomers are nonemissive in both solution and aggregation states; while, the corresponding polymers exhibit intriguing aggregation-induced emission (AIE) characteristics, confirming their PIEgen characteristics. By varying alkynyl substitutions, color-tunable NTIL polymers are achieved with emission wavelength varying from 448 to 498 nm, revealing a series of PIEgens and verifying the importance of modification of NTIL polymers. Further luminescence energy transfer application is carried out as well. This work therefore designs a series of clickable PIEgens and opens a new avenue for the modification of NTIL polymers via click chemistry, which may cause inspirations to the research fields including luminescent polymer, NTIL, click chemistry, AIE and modification.

Versatile Polymerization-Induced Emission Polymers from Barbier Polymerization of Cinnamic Esters with Tunable Emission.

Cinnamic ester is a common and abundant chemical substance, which can be extracted from natural plants. Compared with traditional esters, cinnamic ester contains α,ß-unsaturated carbonyl structure with multiple reactive sites, resulting in more abundant reactivities and chemical structures. Here, a versatile polymerization-induced emission (PIE) is successfully demonstrated through Barbier polymerization of cinnamic ester. Attributed to its abundant reactivities of α,ß-unsaturated carbonyl structure, Barbier polymerization of cinnamic esters with different organodihalides gives polyalcohol and polyketone via 1,2-addition and 1,4-addition, respectively, which is also confirmed by small molecular model reactions. Meanwhile, these organodihalides dependant polyalcohol and polyketone exhibit different non-traditional intrinsic luminescence (NTIL) from aggregation-induced emission (AIE) type to aggregation-caused quenching (ACQ) type, where novel PIE luminogens (PIEgens) are revealed. Further potential applications in explosive detection are carried out, where it achieves TNT detection sensitivity at ppm level in solution and ng level on the test paper. This work therefore expands the structure and functionality libraries of monomer, polymer and NTIL, which might cause inspirations to different fields including polymer chemistry, NTIL, AIE and PIE.

Barbier Polymerization-Induced Emission towards Fully Substituted Polyethylene Analogues with Non-Traditional Intrinsic Luminescence.

The properties of polyethylene are highly dependent on the variety and quantity of substitutions. Generally, polyethylene can only be fully substituted with fluorine atoms, mainly e. g., polytetrafluoroethylene and nafion, because atomic radius of fluorine atom is small enough. The preparation of fully substituted polyethylene analogues (FSPEA) and their non-traditional intrinsic luminescence (NTIL) are attractive, especially for substitutions with relatively larger atomic radii than a fluorine atom. Here, Barbier polymerization-induced emission (PIE) is demonstrated as a universal method for the molecular design of NTIL type FSPEAs with intriguing aggregation-induced emission (AIE) behaviors. Through Barbier polymerization of diphenyldichloromethane and different peroxyesters in the presence of Mg in one pot, a series of FSPEAs, including polytriphenylethanol (PTPE), polydiphenylfurylethanol (PDPFE), polydiphenylthiophenylethanol (PDPTE) and polydiphenylnaphthylethanol (PDPNE) have been successfully prepared. Further potential applications for explosive detection, artificial light-harvesting system and white phosphor-converted light-emitting diode are investigated. Therefore, this work opens up a new approach for the molecular design of FSPEA with non-conjugated luminescence, which may cause inspirations to different research fields like polyolefin and luminescent materials.

Ketyl Radical Anion Mediated Radical Polymerization and Anionic Ring-Opening Polymerization to Give Polymers with Low Molecular Weight Distribution.

The development of novel polymerization capable of yielding polymers with low molecular weight distribution (D) is essential and significant in polymer chemistry, where monofunctional initiator contains only one initiation site in these polymerizations generally. Here, ketyl radical anion species is introduced to develop a novel Ketyl Mediated Polymerization (KMP), which enables radical polymerization at carbon radical site and anionic ring-opening polymerization at oxygen anion site, respectively. Meanwhile, polymerization and corresponding organic synthesis generally couldn't be performed simultaneously in one pot. Through KMP, organic synthesis and polymerization are achieved in one pot, where small molecules (cyclopentane derivates) and polymers with low D are successfully prepared under mild condition simultaneously. At the initiation step, both organic synthesis and polymerization are initiated by single electron transfer reaction with ketyl radical anion formation. Cyclopentane derivates are synthesized through 3-3 coupling reaction and cyclization. Polystyrene and polycaprolactone with low D and a full monomer conversion are prepared by KMP via radical polymerization and anionic ring-opening polymerization, respectively. This work therefore enables both organic synthesis and two different polymerizations from same initiation system, which saves time, labour, resource and energy and expands the reaction mode and method libraries of organic chemistry and polymer chemistry.

One-Pot Synthesis of Stimuli-Responsive Fluorescent Polymers through Polymerization-Induced Emission.

Stimuli-responsive opposite emission (A)/absorption (B) polymer material (A∪B = Ω and A∩B = Ø) represents a novel polymer material that is difficult to prepare. Here, we demonstrate a one-pot strategy for the molecular design of stimuli-responsive opposite emission/absorption polymer material with intriguing properties of opposite emission/absorption and aggregation-induced emission (AIE) type nontraditional intrinsic luminescence (NTIL) in the visible region, through reversible addition-fragmentation chain transfer polymerization-induced emission (PIE) of the N,N-dimethyl-triphenylmethanol moiety. Investigations reveal that NTIL is due to the through-space conjugation effect caused by polymer chain entanglement, when increasing the repeating unit number. The corresponding stimuli-responsive opposite emission/absorption properties are derived from the carbocation-quinoid mechanism, which enables the fluorescence encryption capability. This work therefore demonstrates the proof of concept of a novel opposite emission/absorption polymer material that might cause inspiration in different fields.

Recent Advances and Challenges in Barbier Polymerization.

The Barbier reaction, a classical name reaction for carbon-carbon bond formation, has played important roles in organic chemistry for over 120 years. The introduction of the Barbier reaction into polymer chemistry for the development of a novel Barbier polymerization, expands the methodology, monomer, chemical structure and property libraries of polymerization, aggregation-induced emission (AIE) and non-traditional intrinsic luminescence (NTIL). This mini review focuses on Barbier polymerization, including the brief introduction of the history and importance of polymerization methods design and the achievements of Barbier polymerization from molecular design strategies, functionalities and properties. An outlook of Barbier polymerization is also proposed. This mini review on Barbier polymerization therefore may cause inspirations to scientists in different fields.

Barbier polymerization induced emission of cinnamaldehyde: a one-pot Grignard reaction?

The Barbier reaction is generally regarded as a one-pot Grignard reaction. Here, the Grignard reaction of cinnamaldehyde is demonstrated to give a 1,2-addition product, while the Barbier reaction of cinnamaldehyde yields a macromolecule with interesting aggregation-induced emission type non-conjugated luminescence properties, which indicates that the Barbier reaction cannot be regarded as a one-pot Grignard reaction.

Synthesis of unsymmetrically tetrasubstituted pyrroles and studies of AIEE in pyrrolo[1,2-a]pyrimidine derivatives.

Pyrroles are among the most important heterocycles in pharmaceuticals and agrochemicals. Construction of pyrrole scaffolds with different substituents and a free NH group, however, is challenging. Herein, a metal-free method for the synthesis of unsymmetrically tetrasubstituted NH-pyrroles using a consecutive chemoselective double cyanation is reported. The desired pyrroles were obtained with yields up to 99% and good functional group tolerance. Mechanistic studies identified a reaction mechanism that features a subtle sequence of first cyano-addition and migration, followed by cyano-addition and aromatization to afford the pyrrole skeleton. Pyrrolo[1,2-a]pyrimidines are synthesized as the synthetic applications of NH-pyrroles, and these pyrrolo[1,2-a]pyrimidines exhibit unpredicted time-dependent aggregation-induced emission enhancement (AIEE) properties.

Barbier Hyperbranching Polymerization-Induced Emission from an AB-Type Monomer.

Luminescent polymer materials have gained considerable research efforts in the past decades and are generally molecular designed by extending the π system of the polymer main chain or by incorporating chromophores into the polymer chain, which suffer from poor solubility, difficult synthesis, or multi-step procedures. Meanwhile, according to the step-growth polymerization theory, synthesis of hyperbranched polymers from an AB-type monomer is still challenging. Herein, we report a one-pot synthesis of nonconjugated luminescent hyperbranched polymer material via Barbier hyperbranching polymerization-induced emission (PIE) from an AB-type monomer. The key step in the realization of the hyperbranched polymer is bi-functionalization of a mono-functional group. Through a Barbier reaction between an organohalide and an ester group in one pot, bi-functionalization of mono-functional ester is realized through two-step nucleophilic additions, resulting in hyperbranched polytriphenylmethanols (HPTPM). Attributed to through-space conjugation and inter- and intramolecular charge-transfer effects induced by polymer chain, nonconjugated HPTPMs are PIEgens, which are tunable by monomer structure and polymerization time. When all phenyl groups are rotatable, HPTPM is aggregation-induced emission type PIEgen. Whereas, it is aggregation-caused quenching type PIEgen if some phenyl groups are rotation forbidden. Further potential applications of PIEgen are in the fields of explosive detection and artificial light harvesting systems. This work, therefore, expands the monomer library and molecular design library of hyperbranched polymers through "bi-functionalization of mono-functional group" strategy, which eventually expands the preparation library of nonconjugated luminescent polymer materials through one-pot PIE from nonemissive monomer.

Novel NBN-Embedded Polymers and Their Application as Fluorescent Probes in Fe3+ and Cr3+ Detection.

The isosteric replacement of C═C by B-N units in conjugated organic systems has recently attracted tremendous interest due to its desirable optical, electronic and sensory properties. Compared with BN-, NBN- and BNB-doped polycyclic aromatic hydrocarbons, NBN-embedded polymers are poised to expand the diversity and functionality of olefin polymers, but this new class of materials remain underexplored. Herein, a series of polymers with BNB-doped π-system as a pendant group were synthesized by reversible addition-fragmentation chain transfer (RAFT) polymerization from NBN-containing vinyl monomers, which was prepared via intermolecular dehydration reaction between boronic acid and diamine moieties in one pot. Poly{2-(4-Vinylphenyl)-2,3-dihydro-1H-naphtho[1,8-de][1,3,2]diazaborinine} (P1), poly{N-(4-(1H-naphtho[1,8-de][1,3,2]diazaborinin-2(3H)-yl)phenyl)acrylamide} (P2) and poly{N-(4-(1H-benzo[d][1,3,2]diazaborol-2(3H)-yl)phenyl)acrylamide} (P3) were successfully synthesized. Their structure, photophysical properties and application in metal ion detection were investigated. Three polymers exhibit obvious solvatochromic fluorescence. As fluorescent sensors for the detection of Fe3+ and Cr3+, P1 and P2 show excellent selectivity and sensitivity. The limit of detection (LOD) achieved by Fe3+ is 7.30 nM, and the LOD achieved by Cr3+ is 14.69 nM, which indicates the great potential of these NBN-embedded polymers as metal fluorescence sensors.

Living Covalent-Anionic-Radical Polymerization via a Barbier Strategy.

The developments of the living alkene polymerization method have achieved great progress and enabled the precise synthesis of important polyalkenes with controlled molecular weight, molecular weight distribution, and architecture through an anionic, cationic or radical strategy. However, it is still challenging to develop a living alkene polymerization method through an all-in-one strategy where anionic and radical characteristics are merged into one polymerization species. Here, a versatile living polymerization method is reported by introducing a well-established all-in-one covalent-anionic-radical Barbier strategy into a living polymerization. Through this living covalent-anionic-radical Barbier polymerization (Barbier CARP), narrow distributed polystyrenes, with D as low as 1.05, are successfully prepared under mild conditions with a full monomer conversion by using wide varieties of organohalides, for example, alkyl, benzyl, allyl, and phenyl halides, as initiators with Mg in one pot. This living covalent-anionic-radical polymerization via a Barbier strategy expands the methodology library of polymer chemistry and enables living polymerization with an unconventional polymerization mode.

Unpredicted Concentration-Dependent Sensory Properties of Pyrene-Containing NBN-Doped Polycyclic Aromatic Hydrocarbons.

Pyrene molecules containing NBN-doped polycyclic aromatic hydrocarbons (PAHs) have been synthesized by a simple and efficient intermolecular dehydration reaction between 1-pyrenylboronic acid and aromatic diamine. Pyrene-B (o-phenylenediamine) with a five-membered NBN ring and pyrene-B (1,8-diaminonaphthalene) with a six-membered NBN ring show differing luminescence. Pyrene-B (o-phenylenediamine) shows concentration-dependent luminescence and enhanced emission after grinding at solid state. Pyrene-B (1,8-diaminonaphthalene) exhibits a turn-on type luminescence upon fluoride ion addition at lower concentration, as well as concentration-dependent stability. Further potential applications of Pyrene-B (o-phenylenediamine) on artificial light-harvesting film were demonstrated by using commercial NiR dye as acceptor.

Barbier Self-Condensing Ketyl Polymerization-Induced Emission: A Polarity Reversal Approach to Reversed Polymerizability.

Carbon-carbon bond formation through polarity reversal ketyl radical anion coupling of carbonyls has inspired new reaction modes to this cornerstone carbonyl group and played significant roles in organic chemistry. The introduction of this resplendent polarity reversal ketyl strategy into polymer chemistry will inspire new polymerization mode with unpredicted discoveries. Here we show the successful introduction of polarity reversal ketyl approach to polymer chemistry to realize self-condensing ketyl polymerization with polymerization-induced emission. In this polarity reversal approach, it exhibits intriguing reversed polymerizability, where traditional excellent leaving groups are not suitable for polymerization but challenging polymerizations involving the cleavage of challenging C-F and C-CF3 bonds are realized under mild Barbier conditions. This polarity reversal approach enables the polymer chemistry with polarity reversal ketyl mode, opens up a new avenue toward the polymerization of challenging C-X bonds under mild conditions, and sparks design inspiration of new reaction, polymerization, and functional polymer.

The Introduction of the Radical Cascade Reaction into Polymer Chemistry: A One-Step Strategy for Synchronized Polymerization and Modification.

Polymerization and modification play central roles in polymer chemistry and are generally implemented in two steps, which suffer from the time-consuming two-step strategy and present considerable challenge for complete modification. By introducing the radical cascade reaction (RCR) into polymer chemistry, a one-step strategy is demonstrated to achieve synchronized polymerization and complete modification in situ. Attributed to the cascade feature of iron-catalyzed three-component alkene carboazidation RCR exhibiting carbon-carbon bond formation and carbon-azide bond formation with extremely high efficiency and selectivity in one step, radical cascade polymerization therefore enables the in situ synchronized polymerization through continuous carbon-carbon bond formation and complete modification through carbon-azide bond formation simultaneously. This results in a series of α, ß, and γ poly(amino acid) precursors. This result not only expands the methodology library of polymerization, but also the possibility for polymer science to achieve functional polymers with tailored chemical functionality from in situ polymerization.

Practical Method for Reductive Deuteration of Ketones with Magnesium and D2O.

α-Deuterated alcohols have important applications in pharmaceuticals and mechanism studies. Here, we report a new and practical strategy for the reductive deuteration of ketones using a Mg/BrCH2CH2Br/D2O system, which affords α-deuterated alcohols in good yields and with almost quantitative incorporation of deuterium. The synthetic value of this method has been demonstrated by the easy access to deuterated drugs or drug derivatives. This method may inspire the discovery of other deuterium-containing drugs.

Barbier Hyperbranching Polymerization-Induced Emission toward Facile Fabrication of White Light-Emitting Diode and Light-Harvesting Film.

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.

Promoting water dissociation performance by borinic acid for the strong-acid/base-free hydrogen evolution reaction.

A new type of organic proton donor for the strong-acid/base-free hydrogen evolution reaction is reported, by taking advantage of the electron deficiency of the boron center of borinic acid and the strong affinity and hydrolysis reaction between borinic acid and water with hydrogen ion formation. The borinic acid proton donor exhibits even higher current density than H2SO4 to promote hydrogen evolution performance in DMF.

NBN-Doped Conjugated Polycyclic Aromatic Hydrocarbons as an AIEgen Class for Extremely Sensitive Detection of Explosives.

A simple and efficient synthesis of NBN-doped conjugated polycyclic aromatic hydrocarbons (such as diazaborinines) has been accomplished by a catalyst-free intermolecular dehydration reaction at room temperature between boronic acid and diamine moieties with yields up to 99 %. Polycyclic aromatic hydrocarbons with a six-membered NBN ring are a new class of aggregation-induced emissive luminogens. Extremely 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.

Correction: Synthesis by free radical polymerization and properties of BN-polystyrene and BN-poly(vinylbiphenyl).

Correction for 'Synthesis by free radical polymerization and properties of BN-polystyrene and BN-poly(vinylbiphenyl)' by Wen-Ming Wan et al., Chem. Commun., 2016, 52, 13616-13619.

The introduction of the Barbier reaction into polymer chemistry.

The Barbier reaction, a widely utilized reaction for carbon-carbon bond formation, has played important roles in modern organic chemistry for more than a century. Here, we show its successful introduction to polymer chemistry. Through one-pot Barbier polyaddition (both A2+B2 type and AB type) of monomers containing an organic halide and a benzoyl group, a series of phenylmethanol group containing polymers, including polymonophenylmethanol (PMPM), polydiphenylmethanol (PDPM), and polytriphenylmethanol (PTPM), have been synthesized. Para-PTPM exhibits interesting aggregation-induced emission, tunable thermo-responsive over a wide temperature range, sensory, luminescence enhancement of fluorescent dye in solid-state and processing properties. This significantly expands the libraries of monomer and polymer, and opens up an avenue for the design and application of functional polymer materials.