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Constructing charge transfer (CT) state by introducing donor (D) and acceptor (A) is an efficient strategy to regulate the photophysical properties of luminescent materials. Traditional CT-type luminophores are built on π-conjugated fused-ring structures, which always show hybrid CT/locally excited (LE) states and luminescence quenching effect in the aggregate state. In this work, eight conjugated biphenyl (BP) and nonconjugated diphenylmethane (DPM) derivatives with different donors and acceptors are synthesized to investigate the CT properties. Systematic photophysical characterization and theoretical calculation demonstrate that the through-space CT (TSCT) in nonconjugated DA-DPM exhibit superior photophysical performance than the conjugated DA-BP with through-bond CT (TBCT), the main manifestations are as follows: (1) TSCT luminophores produce longer maximum emission wavelength (λem) than the corresponding TBCT ones. For example, the longest λemof DMA-CN-DPM (DMA, dimethylamino) is 621 nm but the corresponding λemof DMA-CN-BP is only 480 nm. (2) TSCT-based DA-DPM demonstrates more sensitive responsiveness to environmental stimuli such as temperature and polarity. (3) Complete separation of the the highest occupied molecular orbital (HOMO) and the lowest unoccupied molecular orbital (LUMO) distribution exists in all kinds of conformation of DA-DPM, which was hard to realize in conjugated DA-BP.

Making nonconjugated polymers to emit visible light remains a formidable challenge, let alone near-infrared (NIR) light, although NIR luminophores have many advanced applications. Herein, we propose an electron-bridging strategy of using heteroatoms (O, N, and S) to achieve tunable emission from blue to NIR regions (440–800 nm) in nonconjugated polyesters. Especially, sulfur-containing polyester P4exhibits NIR clusteroluminescence (CL) on changing either the concentration or excitation wavelength. Experimental characterization and theoretical calculation demonstrate that the introduction of heteroatoms significantly enhances the through-space interactions (TSIs) viathe electron-bridging effect between heteroatoms and carbonyls. The strength of the electron-bridging effect follows the order of S > N > O, based on two synergistic effects: electronic structure and van der Waals radius of heteroatoms. This work provides a low-cost, scalable platform to produce new-generation nonconjugated luminophores with deeper insight into the photophysical mechanism.

Maleimides have been commonly employed for color reactions in the last few decades, as they produce a bright color when treated with organic or inorganic base. For color formation or the luminescence mechanism, their chromophores have remained unexplored. In this study, we disclosed this well-known phenomenon with commercially available maleimide derivatives based on complex formation between maleimide/succinimide and the organic base of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU). We provided direct experimental evidence of the polymerization process when maleimide is mixed with DBU. The maleimide/DBU complex emits prominent yellow-red fluorescence at long wavelengths due to its through-bond enolate complex formation between the maleimide-based polymer and DBU. DBU can also form an enolate complex with succinimide via a through-space manner, resulting in fluorescence emission similar to that of maleimide does. Their structures were rationally characterized and explored. Additionally, external factors including solvents and the aromatic ring effect can be applied to further stabilize the complex formation, which provides insights for designing novel fluorescent materials.

Interfacial polymerization is a prevalent approach for synthesizing high-performance materials. However, monitoring the polymer growth during this process has posed significant challenges. To overcome this, we have harnessed the aggregation-induced emission effect to enable in situ and real-time observation of the entire interfacial polymerization process. By employing a confocal laser scanning microscope, we have acquired clear images of the polymer and characterized the evolution of its structural heterogeneity, utilizing the environmental sensitivity of the fluorescent AIE moiety. Intriguingly, our study revealed that the polymer density is higher away from the interface, in contrast to the expected homogeneity. The changing ratio of the two monomers in the reaction region accounts for this density gradient. Additionally, we have demonstrated the precise growth kinetics of the polymer under various conditions. Our results provide a novel platform for elucidating the mechanisms and properties of interfacial polymerization.

Noncovalent interactions play an increasingly essential role in manipulating the photophysical properties of poorly conjugated luminogens, especially in the aggregate and solid states. In a recent study published in the Journal of the American Chemical Society, McGonigal, Jones, Moggach, and co-workers provide solid structure-property evidence on how subtle structural changes and noncovalent interactions colorize the photophysical properties of fluorescent organic molecular rotors under high pressure.

Room-temperature phosphorescence (RTP) is a photophysical phenomenon typically associated with a long-lived emission that can be detected by the unaided eye. Several natural proteins display RTP, as do certain artificial polymers. In both cases, the RTP is ascribed to effective intramolecular through-space electronic communication. However, small molecules with internal electronic communication that enable RTP are relatively rare. Herein, we describe an alkyl halide-responsive RTP system consisting of a meta-formylphenyl-bearing pillar[5]arene derivative that supports effective through-space charge transfer (TSCT) within the pillararene cavity. Treatment with bromoethane, a heavy atom-containing guest for the pillar[5]arene host, serves to enhance the emission. An isomeric para-formylphenyl-bearing pillar[5]arene system proved ineffective in producing an RTP effect. Quantum chemical calculations based on single-crystal X-ray diffraction analyses provided insights into the structural determinants governing TSCT between the 1,4-dimethoxybenzene donor units and the formylphenyl groups of the pillar[5]arene, as well as the associated energy gaps and intersystem crossing channels. We believe that the present system and the associated mechanistic analysis provide the foundation for design of new small molecule with tunable RTP features.

Conventional hydrogels such as polyacrylamide and polyacrylic acid ones seldom exhibit phosphorescences at ambient conditions, which limit their applications as optical materials. We propose and demonstrate here a facile strategy to afford these hydrogels with room-temperature phosphorescence by polymerization-induced crystallization of dopant molecules that results in segregation and confinement of the gel matrix with carbonyl groups and thus clusterization-induced phosphorescence. As a model system, crown ethers (CEs) are dissolved in an aqueous solution of concentrated acrylamide that greatly increases the solubility of CEs. During the polymerization process, CEs crystallize to form large spherulites in the polyacrylamide hydrogel. The crystallization arises from the drastically reduced solubility of CEs after the conversion of monomers to polymers during the gel synthesis. The resultant composite hydrogel with a water content of 67 wt % exhibits extraordinary phosphorescence behavior yet maintains good stretchability and resilience. We found that the partial gel matrix is squeezed and confined by in situ-formed crystals, leading to carbonyl clusters and thus phosphorescence emission. The composite gel shows green phosphorescence with an emission peak at 512 nm and a lifetime of 342 ms. The afterglow emission is detectable by the naked eye for several seconds. This strategy has good universality, as validated in other hydrogels with different polymeric matrices and dopant molecules. The development of hydrogels with good mechanical and phosphorescent properties should merit the design of multifunctional soft machines with applications in biomedical and engineering fields.

We demonstrate a unique mechano-luminochromic (MLC) effect of an aggregation-induced emission (AIE)-active luminogen (AIEgen), DTPE-TB, which is characterized by the evidently changed emission intensity but unimpressively shifted emission colors of the molecular solid. This behavior is termed mechanofluoro enhancement (MFE), which is quite distinct from the commonly reported AIEgens with the MLC property. The MFE effect originates from the special design of the DTPE-TB molecule, in which the two tetraphenylethene (TPE) units play the role of AIE, and the Tröger’s base unit takes the part of a mechanical force supporter. Therefore, when the DTPE-TB molecular solid is subjected to mechanical forces, the Λ-shaped Tröger’s base unit releases external forces by changing its dihedral angle. Meanwhile, the TPE units nearly keep unchanged in the molecular arrangement. Accordingly, the DTPE-TB solid shows an evidently enhanced emission under pressure due to the aggravated restriction of intramolecular motions but a slightly shifted emission wavelength due to the tiny variations in molecular packing.

It remains a great challenge to design and synthesize organic luminescent molecules with strong emission in both dilute solution and aggregate state. Herein, an organic cage with dodecadansyl groups (D-RCC1) from an easy sulfonation reaction displays strong emissive behavior in dilute organic solution with a quantum yield of 42%. Moreover, D-RCC1 exhibits an ultrahigh quantum yield of 92% in the solid state, which is more than 3 times that of 27% for the model compound D-DEA. The results of the experiment and theoretical calculation show that the three-dimensional symmetrical skeleton of the organic cage anchored evenly by multiple dye molecules effectively satisfies both high local density and a symmetrical distribution of chromophores, which prevents the interaction of dye molecules and ensures that dye molecules have strong emission in both single-molecule and aggregate states.

Nonconjugated and nonaromatic heteroatoms‐based structures are discovered with visible emission at clustering state, namely clusteroluminogens (CLgens). Such kind of luminescence is termed clusteroluminescence (CL) which could not be explained by the traditional molecular photophysical theories constructed upon through‐bond conjugation, so investigation on CL has great theoretical significance. In this perspective, we summarize a general feature for C═O bond‐based CLgens that a magic blue emission around 440 nm widely exists in different systems such as natural protein, polyamide, polyester, and polyketone. Comprehensive analysis of the reported works suggests that the (n, π*) transition of carbonyl group most likely generates the 440 nm CL. This perspective aims to draw researchers' attention to the common features and general photophysical theories of CL, and shine new light on aggregate photophysics.

Multicomponent polymerization (MCP) has received worldwide attention as a powerful synthetic strategy for various polymers with complex structures. However, few studies have been reported to fully utilize the monomer combination diversity of MCPs to facilitate the synthesis of diversified polymers with novel structures and advanced functionalities. Herein, we report a facile multicomponent polymerization route based on the diversity-oriented synthesis. Using varying combinations of difunctionalizable alkynes, sulfonyl azides, and Schiff bases, diverse functional polymers with multisubstituted small heterocycles are successfully produced. High stereoselectivity is observed on specific polymeric products. The obtained azetidine-derivative heterocycles exhibit high stability even after treatment with extra HCl and KOH for 48 h. Additionally, polymers with tetraphenylethylene moieties show strong aggregation-induced emission and can function as promising chemosensors for detecting Pd2+and Cr2O72–. The presented facile MCP routes can bring new inspiration to polymer chemistry, and the fascinating functionalities of the obtained polymers with stable four-membered heterocycles can promote further research on the design, modification, and applications of diversified functional polymer materials.

Electronic conjugation through covalent bonds is generally considered as the basis for the electronic transition of organic luminescent materials. Tetraphenylethylene (TPE), an efficient fluorophore with aggregation-induced emission character, fluoresces blue emission in the aggregate state, and such photoluminescence is always ascribed to the through-bond conjugation (TBC) among the four phenyl rings and the central C═C bond. However, in this work, systematic spectroscopic studies and DFT theoretical simulation reveal that the intramolecular through-space interaction (TSI) between two vicinal phenyl rings generates the bright blue emission in TPE but not the TBC effect. Furthermore, the evaluation of excited-state decay dynamics suggests the significance of photoinduced isomerization in the nonradiative decay of TPE in the solution state. More importantly, different from the traditional qualitative description for TSI, the quantitative elucidation of the TSI is realized through the atoms-in-molecules analysis; meanwhile, a theoretical solid-state model for TPE and other multirotor systems for studying the electronic configuration is preliminarily established. The mechanistic model of TSI delineated in this work provides a new strategy to design luminescent materials beyond the traditional theory of TBC and expands the quantum understanding of molecular behavior to the aggregate level.

Organic radicals are unstable and stable radicals usually display non-luminescent properties. Luminescent radicals possess the all-in-one properties of optoelectronics, electronics, and magnetics. To date, the reported structures of luminescent radicals are limited to triphenylmethyl radical derivatives and their analogues, which are stabilized with extended π-conjugation. Here, we demonstrate the first example of a nonconjugated luminescent radical. In spite of the lack of delocalized π-stabilization, the radical polymer readily emits red luminescence in the solid state. A traditional luminescent quencher, 2,2,6,6-tetramethylpiperidin-1-yl turned into a red chromophore when grafted onto a polymer backbone. Experimental data confirm that the emission is associated with the nitroxide radicals and is also affected by the packing of the polymer. This work discloses a novel class of luminescent radicals and a distinctive pathway for luminescence from open-shell materials.

Conventional π-conjugated luminophores suffer from problems such as emission quenching, biotoxicity, environmental pollution, etc. The emerging nonconjugated and nonaromatic clusteroluminogens (CLgens) are expected to overcome these stubborn drawbacks, so research of CLgens shows great significance not only for practical application but also for the construction of fundamental photophysical theories. This perspective summarizes the unusual features of CLgens in comparison to traditional chromophores, such as nonconjugated molecular structures, unmatched absorption and excitation, excitation-dependent luminescence, multiple emission peaks, and room-temperature phosphorescence. Different from the theory of through-bond conjugation in π-conjugated luminophores, through-space interactions, including through-space n···n interaction and through-space n···π interaction, are regarded as the emitting sources of nonconjugated CLgens. In addition, the formation of network clusters is proposed as an efficient strategy to improve the performance of CLgens, and their potential applications of anticounterfeiting, photoelectronic devices, and bioimaging are prospected.

Dendrimers, as the latest generation of artificial macromolecules, have aroused great attention in the field of clusteroluminescence owing to their unique structural and photophysical features. However, previously reported dendrimers with cluster-oluminescenence property usually contain πelectrons-involved carbonyl groups and/or environment-sensitive aliphatic amine moieties in their structures, thus complicating the interpretation of the emission process. On the other hand, a systematic investigation on the luminescence performance of dendrimers with diverse generations is significantly important for the researchers to gain further mechanistic insights into the clusteroluminescence, but has still been scarcely touched. In this contribution, we reported a series of oxygen and sulfur-based pure n-electron dendrimers with different generations from G1 to G3. Benefiting from the highly-branched three-dimensional crowded molecular structures, all these dendrimers exhibited bright fluorescence emission in visible light region due to their prominent clusteroluminescence property. Moreover, the fluorescence intensity and emission wavelength were simultaneously boosted as their generation increased due to the more crowded molecular architectures, as well as the formation of tighter and larger clusters at higher generation. Besides, these dendrimers also showed concentration- and aggregation-enhanced luminescence behaviors, presenting typical aggregation-induced emission (AIE) nature. Coupled with remarkable water solubility and biocompatibility as well as the excellent photostability, the G3 dendrimer selected as a representative was successfully applied in the multicolor cell imaging. In addition, the G3 dendrimer was also proved to be capable of acting as a molecular ruler to detect specific-sized molecule in aqueous solutions. This work not only validated the rationality of the clusteroluminescence mechanism but also offered high-performance clusteroluminogens for practical application.

Apart from the traditional through-bond conjugation (TBC), through-space conjugation (TSC) is gradually proved as another important interaction in photophysical processes, especially for the recent observation of clusteroluminescence from nonconjugated molecules. However, unlike TBC in conjugated chromophores, it is still challenging to manipulate TSC and clusteroluminescence. Herein, simple and nonconjugated triphenylmethane (TPM) and its derivatives with electron-donating and electron-withdrawing groups were synthesized, and their photophysical properties were systematically studied. TPM was characterized with visible clusteroluminescence due to the intramolecular TSC. Experimental and theoretical results showed that the introduction of electron-donating groups into TPM could red-shift the wavelength and increase the efficiency of clusteroluminescence simultaneously, due to the increased electronic density and stabilization of TSC. However, TPM derivatives with electron-withdrawing groups showed inefficient or even quenched clusteroluminescence caused by the vigorous excited-state intramolecular motion and intermolecular photoinduced electron transfer process. This work provides a reliable strategy to manipulate TSC and clusteroluminescence.

Solid-state molecular motions (SSMM) play a critical role in adjusting behaviors and properties of materials. However, research on SSMM, especially for multicomponent systems, suffers from various problems and is rarely explored. Herein, through collaboration with cocrystal engineering, visualization and manipulation of SSMM in two-component systems, namely, FSBO ((E)-2-(4-fluorostyryl)benzo[d]oxazole)/TCB (1,2,4,5-tetracyanobenzene) and PVBO ((E)-2-(2-(pyridin-4-yl)vinyl)benzo[d]oxazole)/TCB, were realized. The obtained yellow-emissive F/T (FSBO/TCB) cocrystal displayed turn-on fluorescence, and the green-emissive P/T (PVBO/TCB) cocrystal presented redder emission, both of which exhibited an aggregation-induced emission property. At varied pressure and temperature, the grinding mixtures of FSBO/TCB and PVBO/TCB displayed different molecular motions that were readily observed through the fluorescence signal. Notably, even without grinding, FSBO and TCB molecules could move over for 4 mm in a 1D tube. The unique emission changes induced by SSMM were applied in information storage and dynamic anticounterfeiting. This work not only visualized and manipulated SSMM but offered more insights for multicomponent study in aggregate science.

Air-stable organic radicals and radical ions have attracted great attention for their far-reaching application ranging from bioimaging to organic electronics. However, because of the highly reactive nature of organic radicals, the design and synthesis of air-stable organic radicals still remains a challenge. Herein, an air-stable organic radical from a controllable photoinduced domino reaction of a hexa-aryl substituted anthracene is described. The domino reaction involves a photoinduced [4 + 2] cycloaddition reaction, rearrangement, photolysis, and an elimination reaction; 1H/13C NMR spectroscopy, high resolution mass spectrometry, single-crystal X-ray diffraction, and EPR spectroscopy were exploited for characterization. Furthermore, a photoinduced domino reaction mechanism is proposed according to the experimental and theoretical studies. In addition, the effects of employing push and pull electronic groups on the controllable photoinduced domino reaction were investigated. This article not only offers a new blue emitter and novel air-stable organic radical compound for potential application in organic semiconductor applications, but also provides a perspective for understanding the fundamentals of the reaction mechanism on going from anthracene to semiquinone in such anthracene systems.

In 2023, The MOE Key Laboratory of Macromolecular Synthesis and Functionalization in Zhejiang University had achieved several important results in the five research directions. First, for controllable catalytic polymerization, a new silicon-centered organoboron binary catalyst was developed for copolymerization of epoxides, and a series of cooperative organocatalysts were proposed for ring-opening copolymerization of chalcogen-rich monomers. Second, with respect to microstructure and rheology, axially encoded metafiber demonstrated its capacity for integrating multiple electronics, while artificial nacre materials showed improved strength and toughness due to interlayer entanglement. Third, concerning separating functional polymers, interfacial polymerization was monitored via aggregation-induced emission, and vacuum filtration was applied to assist interfacial polymerization. Fourth, in terms of biomedical functional polymers, we designed antibacterial materials such as a novel quaternary ammonium salt that enables polyethylene terephthalate recycling and its antibacterial function, nanozyme-armed phage proved its efficiency in combating bacterial infection, and also transition metal nanoparticles showed capacities in antibacterial treatments. We also made achievements in biomedical materials, including polymeric microneedles for minimally invasive implantation and functionalization of cardiac patches, as well as ROS-responsive/scavenging prodrug/miRNA balloon coating to promote drug delivery efficiency. Besides, methods and mechanisms of RNA labeling has been developed. Fifth, about photo-electro-magnetic functional polymers, through-space conjugation was successfully manipulated by altering subunit packing modes, room-temperature phosphorescent hydrogels were synthesized via polymerization-induced crystallization of dopant molecules, and single crystals of both fullerene and non-fullerene acceptors were grown in crystallized organogel, with their photodetection performance further explored. The related works are reviewed in this paper.

Full-color luminophores have advanced applications in materials and engineering, but constructing color-tunable clusteroluminescence (CL) from nonconjugated polymers based on through-space interactions remains a huge challenge. Herein, we develop phosphine-capped nonconjugated polyesters exhibiting blue-to-red CL (400–700 nm) based on phosphine-initiated copolymerization of epoxides and cyclic anhydrides, especially P1-0.5TPP, which exhibits red CL (610 nm) with a high quantum yield of 32%. Experiments and theoretical calculations disclose that the phosphine-capped effect in polyesters brings about conformational changes and induces phosphine–ester clusters by through-space (n,π*) interactions. Moreover, CL colors and efficiencies can be easily tailored by types of phosphines, compositions and structures of polyesters, and concentration. Significantly, the role of polymer motions (group, segmental, and chain motions) on CL originating from microregions inside polyesters is revealed. Further, phosphine-capped nonconjugated polyesters are demonstrated to be nonconjugated dyes and fluorescent fibers and are also used for multicolor light-emitting diodes including white light. This work not only provides an engineering strategy based on the end-group effect to prepare full-color clusteroluminogens but also broadens the prospects for material applications.

Luminescent molecules with aggregation-induced emission (AIE) property or AIE-active luminogens (AIE-gens) are typical stimuli-responsive materials. Many AIE-gens have shown luminescent responses to mechano-, thermo-, electro-, vapo-, and/or solvato-stimulus, but the detailed structure–property relationship has been addressed for only a few of them. Here, we report a tetraphenylethene (TPE) derivative with pyridyl modifiers and ethynylene bridges. The (Z)- and (E)-isomers are clearly purified, and both of them are AIE-active and demonstrate multiple luminescent responses to external stimuli. Distinct from other reported TPE derivatives, the two isomers show negative solvatochromism due to the large dipole in the ground electronic state. By correlating with the single crystal structures, the subtle differences in quantum efficiency and emission peak wavelength of the solids of the (Z)- and (E)-isomers are rationally explained. Moreover, the ground powder of the (E)-isomer can recover its emission color from green to blue in the air at room temperature but the (Z)-isomer cannot. This difference is interpreted by a mechanism of water-triggered conformational variation, which depends on the hydrogen bond formation between pyridyl moieties and water molecules in the air. In addition to the reversible emission color changes by cyclic grinding–fuming treatments, both of the isomers exhibit a reversible luminescent response to acid–base treatments by switching the emission color between green (basic) and yellow (acid), owing to the incorporation of pyridyl units into the molecule. The unprecedented multiple stimuli-responsive behaviors and clear mechanism explanations allow this kind of AIE-gens to be promising smart materials.

Sulfur, which is generated from the waste byproducts in the oil and gas refinery industry, is an abundant, cheap, stable, and readily available source in the world. However, the utilization of excessive amounts of sulfur is mostly limited, and developing novel methods for sulfur conversion is still a global concern. Here, we report a facile one-step conversion from elemental sulfur to functional poly(O-thiocarbamate)s through a multicomponent polymerization of sulfur, diols, and diisocyanides, which possesses a series of advantages such as mild condition (55 °C), short reaction time (1 h), 100% atom economy, and transition-metal free in the catalyst system. Seven poly(O-thiocarbamate)s are constructed with high yields (up to 95%), large molecular weight (up to 53100 of Mw), good solubility in organic solvents, and completely new polymer structures. The poly(O-thiocarbamate)s possess a high refractive index above 1.7 from 600 to 1700 nm by adjusting the sulfur content. By incorporating tetraphenylethene (TPE) moieties into the polymer structure, the poly(O-thiocarbamate)s can also be designed as fluorescent sensors to detect harmful metal cation of Hg2+in a turn-on mode with high sensitivity (LOD = 32 nM) and excellent selectivity (over interference cations of Pb2+, Au3+, Ag+). Different from the previous reports, the exact coordination structure is first identified by single-crystal X-ray diffraction, which is revealed in a tetracoordination fashion (two sulfur and two chloride) using a model coordination compound.

Circularly polarized luminescence (CPL) switching has attracted great attention due to the potential applications in chiral photonics and electronics. However, the lack of examples to achieve switchable CPL within a single material in the dry solid state hampers the scope of applications. Herein, we demonstrate a crystalline chiral polymer film as a polarizing medium consisting of radially assembled twisted crystallites, where achiral aggregation-induced emissive luminogens (AIEgens) are confined between the twisted crystalline stacks, eventually yielding handedness-switchable CPL by simple film tilting. Hierarchically organized twisted crystallites create the selective reflection activity of the polarizing medium. Upon film tilting, enantiomeric switching is realized by selectively collecting transmitted and reflected CPL components. The confined AIEgens in the crystalline polarizing system show a great enhancement of the luminescence efficiency. Moreover, the approach is general with broadband activity, and various AIEgens could be applied to generate full-color-tunable CPL. Additionally, the rigid and continuous nature of this polarizing system affords enhanced optical stability and facile modulation, developing a general route for designing chiroptical materials.

Mechanochromic (MC) luminogens in response to external stimulus have shown promising applications as pressure sensors and memory devices. Meanwhile, research on their underlying mechanism is still in the initial stage. Here, three pyridinium-functionalized tetraphenylethylenes bearing n-pentyloxy, hydrogen and nitro groups, namely TPE-OP, TPE-H and TPE-NO, are designed to systematically investigate the influence of the push–pull electronic effect and molecular conformation on MC luminescence. Upon anisotropic grinding and isotropic hydrostatic compression, TPE-OP with strong intramolecular charge transfer (ICT) affords the best MC behavior among them. Analysis of three polymorphs of TPE-H clearly indicates that planarization of the molecular conformation plays an important role in their bathochromic shifts under mechanical stimuli. Theoretical calculations also verify that high twisting stress of AIEgens can be released under high pressure. This study presents a mechanistic insight into MC behaviour and an effective strategy to achieve high-contrast MC luminescence.

The brightness of organic fluorescence materials determines their resolution and sensitivity in fluorescence display and detection. However, strategies to effectively enhance the brightness are still scarce. Conventional planar π-conjugated molecules display excellent photophysical properties as isolated species but suffer from aggregation-caused quenching effect when aggregated owing to the cofacial π–π interactions. In contrast, twisted molecules show high photoluminescence quantum yield (ΦPL) in aggregate while at the cost of absorption due to the breakage in conjugation. Therefore, it is challenging to integrate the strong absorption and high solid-state ΦPL, which are two main indicators of brightness, into one molecule. Herein, we propose a molecular design strategy to boost the brightness through the incorporation of planar blocks into twisted skeletons. As a proof-of-concept, twisted small-molecule TT3-oCB with larger π-conjugated dithieno[3,2-b:2′,3′-d]thiophene unit displays superb brightness at the NIR-IIb (1500–1700 nm) than that of TT1-oCB and TT2-oCB with smaller thiophene and thienothiophene unit, respectively. Whole-body angiography using TT3-oCB nanoparticles presents an apparent vessel width of 0.29 mm. Improved NIR-IIb image resolution is achieved for femoral vessels with an apparent width of only 0.04 mm. High-magnification through-skull microscopic NIR-IIb imaging of cerebral vasculature gives an apparent width of ∼3.3 μm. Moreover, the deeply located internal organ such as bladder is identified with high clarity. The present molecular design philosophy embodies a platform for further development of in vivobioimaging.

Semiconducting polymer nanoparticles (SPNs) emitting in the second near-infrared window (NIR-II, 1000–1700 nm) are promising materials for deep-tissue optical imaging in mammals, but the brightness is far from satisfactory. Herein, we developed a molecular design strategy to boost the brightness of NIR-II SPNs: structure planarization and twisting. By integration of the strong absorption coefficient inherited from planar π-conjugated units and high solid-state quantum yield (ΦPL) from twisted motifs into one polymer, a rise in brightness was obtained. The resulting pNIR-4 with both twisted and planar structure displayed improved ΦPLand absorption when compared to the planar polymer pNIR-1 and the twisted polymer pNIR-2. Given the emission tail extending into the NIR-IIa region (1300–1400 nm) of the pNIR-4 nanoparticles, NIR-IIa fluorescence imaging of blood vessels with enhanced clarity was observed. Moreover, a pH-responsive poly(β-amino ester) made pNIR-4 specifically accumulate at tumor sites, allowing NIR-IIa fluorescence image-guided cancer precision resection. This study provides a molecular design strategy for developing highly bright fluorophores.

The development of a facile and efficient polymerization method to prepare polymers with unique nontraditional intrinsic luminescent (NTIL) properties is of vital importance and highly desired. In this work, a multicomponent tandem polymerization of alkyne and amines for the efficient preparation of NTIL poly(aminomaleimide)s (PAMIs) was established. Soluble and thermally stable PAMIs with acceptable molecular weights and well-defined structures are obtained in excellent yields after optimization. Sequence-controlled PAMIs with well-defined structures are obtained by using secondary amines for the amino–yne click reaction. The resulting amino-terminated PAMIs can be used as macromonomers for further polymerization. The PAMIs exhibit NTIL properties, and their emission in dimethyl sulfoxide/H2O mixtures can be tailored by changing the length of hydrophobic linker. Additionally, they exhibit low cytotoxicity and can be used as fluorescent bioprobes for bioimaging applications. Considering the mild polymerization conditions, readily available monomers, and excellent product performance, the present multicomponent tandem polymerizations opens up a new avenue to prepare functional polymeric materials with NTIL properties.

To achieve super-resolution imaging in biological research using stimulated emission depletion (STED) nanoscopy, organic luminescent materials and their corresponding fluorescent nanoparticles with high brightness and photostability are of great significance. Herein, donor-acceptor-typed DBTBT-4C8 bearing flexible alkyl chains was developed, not only to afford deep-red emission from 600 to 800 nm but also to obtain high fluorescent brightness with the absolute photoluminescence quantum yields of 25%. After that, well-defined and monodispersed spherical nanoparticles using DBTBT-4C8 with bright emission, excellent biocompatibility, and photostability, which can easily mix with amphipathic block polymers, were then produced for super-resolution in vitro and in vivo imaging using STED nanoscopy. The observations showed that in contrast to confocal microscopy with a full width at half-maximum (FWHM) value of ≈400 nm, superior resolution with a significantly improved FWHM value of only 100 nm was achieved in biomedical cell imaging, which was also used to reconstruct three-dimensional images of stained HeLa cells at an ultrahigh resolution. More importantly, by using the prepared fluorescent organic nanoparticles (FONPs) in STED nanoscopy, in vivo imaging in glass catfish with largely enhanced resolution was also successfully achieved, demonstrating that these developed deep-red FONPs here are highly suitable for super-resolution in vitro and in vivo imaging using STED nanoscopy.

There is still an urgent demand for novel smart materials that can achieve a diverse range of practical applications in the synthetic material area. Herein, we developed a simple but versatile aggregation-induced emission luminogen (AIEgen, 1). Compound 1was sensitive to an electric stimulus and displayed reversibly three-color switched electrochromism and on-to-off electroluminochromism. Such properties allowed the fabrication of high-performance non-doped OLEDs with a high external quantum efficiency of 5.22%. Due to its AIE property and remarkable sensitive color change in response to polarity change, it can serve as a unique imaging probe for detecting environmental polarity in cells and selective visualization of lipid droplets in live tissues. More impressively, compound 1exhibited a wide range of thermoresponsive behaviors with a ratiometric luminescence change and noticeable fluorescence color switching. As another remarkable feature, it can respond to anisotropic shearing force and isotropic hydrostatic pressure with prominent and contrasting luminescence conversion due to the distinct disturbance of the weak intermolecular interactions and charge transfer process. The present results may offer an important guideline for multifunctional molecular design and provide an important step forward to expand the real-life applications of smart materials.

In situphoto-irradiation of trans-2-(4-fluorostyryl)benzo[d]oxazole (t-FSBO) and trans-2-(2,4-difluorostyryl)benzo[d]oxazole (t-2FSBO) with aggregation-caused quenching (ACQ) characteristics in the solid-state afforded unprecedented aggregation-induced emission (AIE) luminogens through [2+2] cycloaddition. Although the photoreaction products were weakly conjugated, they were emissive. Interestingly, the product cisoid-2,2′-(3,4-bis(2,4-fluorophenyl)cyclobutene-1,2-diyl)bis(benzo[d]oxazole) (c-2FPCBO) could form blue and yellow emissive crystals due to the different packing modes. Crystallographic results and computational calculation suggested that this anomalous phenomenon was attributed to intramolecular and intermolecular through-space conjugation. To the best of our knowledge, this is the first reported in situACQ-to-AIE transformation achieved by UV irradiation, deepening the understanding that non-conjugated molecules can be emissive. In addition to this novel and accessible ACQ-to-AIE transformation, the photosalient effect was also observed during the reactions. Notably, a macroscopic actuator was achieved by simply coating t-FSBO on a nitrile butadiene glove, which could bend over 70° towards UV light source. This system thus offers a new class of AIE luminogens with a “living” character.

Unorthodox luminescent polymers without large π-conjugated structures, as promising soft luminescent materials, have recently received considerable attention owing to the availability of versatile preparation methods and their good processability. These polymers generally possess electron-rich moieties, with a diversity of intermolecular and intramolecular interactions through delocalized electrons. Therefore, polymerization itself can be an effective way to realize fluorescence emission. Here, polymerization-induced emission (PIE) is conceptualized as the process of transforming non-luminescent small molecules (i.e., monomers) into luminescent polymers. Correspondingly, PIE luminogens (PIEgens) with luminescent clusters, which are proposed as group aggregates with the minimum critical size for emission, require further investigation in order to understand the structure–emission relationships and related mechanisms. Promisingly, advanced polymerization methods offer unlimited opportunities to develop new soft luminescent polymers owing to the multi-level structures of polymers.

Simple, rapid, and sensitive assays of DNA sequence hold great importance in genetic analysis, clinical diagnosis, and molecular biology research. Most current methods for DNA detection, based on the complementary base pairing, require hybridization with intricately modified single-stranded DNA (ssDNA) probes or analytes. Herein, we have developed a powerful molecule with aggregation-induced emission (AIE) characteristic, namely, TPBT, which can specifically recognize double-stranded DNA (dsDNA) by emitting out a unique dual-color fluorescent signal of red (∼640 nm) and green (∼537 nm). The red-color emission at around 640 nm is observed when TPBT binds with dsDNA, ssDNA, proteins, and other polyanionic analytes. However, the green emission at around 537 nm is demonstrated to be the exclusive response of TPBT to dsDNA, which is closely related to the conformational change of TPBT upon groove binding. More strikingly, TPBT can distinguish single-nucleotide polymorphisms (SNPs) in a dsDNA sequence and detect the DNA damage suffered from UV light with ultrahigh sensitivity and specificity. This label-free, AIEgen-based dsDNA assay method is facile, robust, and universal, which will lead to major advances in genomic and disease diagnosis.

Synthetic polymerization and supramolecular polymerization with sequence control are far from an easy task. Herein, a narcissistic self-sorting supramolecular polymer is prepared with a sequence of (−AA–BB−)nby using cucurbit[8]uril (CB[8])-based ternary complexes as supramolecular monomers, which are spontaneously formed from heteroditopic AB-type guest and CB[8]. Supramolecular polymerization and the structural changes at each stage of polymerization have been successfully demonstrated by NMR, UV–vis, and fluorescence spectra. The self-sorting starts from the second step of polymerization after the formation of different ternary complexes as supra-monomers. The dynamic supramolecular interactions and the thermodynamic stability of the host–guest complexes are found to be the crucial factors to drive the sequence control of the supramolecular polymers. Furthermore, the water-soluble supramolecular polymer is red-emissive and can serve as a fluorescent sensor to detect morphine in artificial urine with considerable stability, sensitivity, and accuracy. And it can also distinguish heroin and morphine, two kinds of opioids with similar structures.

Efficient photoisomerization of chromophores is important in living systems, and structural constraints of protein pocket on chromophores are the probable reason for moving their dynamic reaction equilibrium forward. On the other hand, photochemical reaction to switch a molecule from one isomer to the other with different geometry and property in a high yield will continue to play a vital role in the synthetic chemistry and material science. Because of the important role of efficient photoisomerization, a biomimetic approach for “seeing” and controlling the photoisomerization is developed by using the technology of aggregation-induced emission (AIE) with supramolecular chemistry. It is revealed that a (Z)-isomer of a 2-ureido-4[1H]-pyrimidinone-containing tetraphenylethene (TPE-UPy) can be photoisomerized into supramolecular polymer form of its (E)-counterpart in chloroform in a high reaction yield of 68.1%. The yield is further enhanced to 100% in THF as aggregates of supramolecular polymers of (E)-TPE-UPy are formed, which completely inhibits the reverse photoreaction to form (Z)-TPE-UPy. In chloroform with organic acid, a mixture of equal amounts of (E)- and (Z)-isomers was obtained due to the disruption of the formation of intermolecular hydrogen bonds. The AIE characteristics of the isomers allow us to directly “see” the “turn-on” photoisomerization process by distinct fluorescence color changes, and the photoisomerization observed here may enable the development of a promising generation of optical power limiting materials.

Organic fluorophores for stimulated emission depletion (STED) nanoscopy usually suffer from quenched emission in the aggregate state and inferior photostability, which largely limit their application in real-time, in situ, and long-term imaging at an ultrahigh resolution. Herein, an aggregation-induced emission (AIE) luminogen of DP-TBT with bright emission in solid state (photoluminescence quantum yields = 25%) and excellent photostability was designed to meet the requirements in STED nanoscopy. In addition to its excellent fluorescence properties, DP-TBT could also easily form self-assembling helixes and finally be well-visualized by super-resolution STED nanoscopy. The observations showed that helical fibers of DP-TBT as dashed lines had a much decreased fiber width with also a full width at half-maximum value of only 178 nm, which is ∼6 times higher than solid lines obtained by confocal microscopy (1154 nm). The STED nanoscopic data were also used to reconstruct 3D images of assembled helixes. Finally, by long-term tracking and dynamic monitoring, the formation and growth of helical fibers by DP-TBT in self-assembly processes were successfully obtained. These findings imply that highly emissive AIEgens with good photostability are highly suitable for real-time, in situ, and dynamic imaging at super-resolution using STED nanoscopy.

Cancer immunotherapy is a favorable strategy for facilitating anti‐tumor immunity, but it shows limited benefits in clinical practice owing to the immunosuppressive tumor microenvironment. Pyroptosis shows great immunostimulatory effect on tumor, whereas the lack of pyroptotic inducer with imaging property has restricted its progress in tumor theranostics. Herein, a mitochondria‐targeted aggregation‐induced emission (AIE) luminogen (TPA‐2TIN) with NIR‐II emission is designed for highly efficient induction of tumor cell pyroptosis. The fabricated TPA‐2TIN nanoparticles can be efficiently taken up by tumor cells and selectively accumulated in tumor for a long term observed by NIR‐II fluorescence imaging. More importantly, the TPA‐2TIN nanoparticles can effectively stimulate immune responses both in vitro and in vivo mediated by the mitochondrial dysfunctions and the subsequent activation of the pyroptotic pathway. Ultimately, the reversal of the immunosuppressive tumor microenvironment significantly enhances the immune checkpoint therapy. This study paves a new avenue for adjuvant immunotherapy of cancer. A NIR‐II aggregation‐induced emission (AIE) luminogen is encapsulated with polymers to form water‐soluble nanoparticles for fluorescence‐guided tumor immunotherapy. With strong accumulation in mitochondria, the TPA‐2TIN nanoparticles induce the release of cytochrome c from mitochondria and activate caspase 3, resulting in the cleavage of Gasdermin E and initiation of cell pyroptosis. Pyroptotic cells activate the immune responses, promoting the immune checkpoint therapy effectively.

Acrylonitriles with aggregation-induced emission (AIE) characteristics have been found to show promising applications in two-photon biomedical imaging. Generally, elaborate synthetic efforts are required to achieve different acrylonitriles with distinct functionalities. In this work, we first reported the synthesis of two different group-functionalized AIE-active acrylonitriles (TPAT-AN-XF and 2TPAT-AN) obtained simply by mixing the same reactants at different temperatures using a facile and transition metal-free synthetic method. These two AIE luminogens (AIEgens) exhibit unique properties such as bright red emission in the solid state, large Stokes shift, and large two-photon absorption cross section. Water-soluble nanoparticles (NPs) of 2TPAT-AN were prepared by a nanoprecipitation method. In vitro imaging data show that 2TPAT-AN NPs can selectively stain lysosome in live cells. Besides one-photon imaging, remarkable two-photon imaging of live tumor tissues can be achieved with high resolution and deep tissue penetration. 2TPAT-AN NPs show high biocompatibility and are successfully utilized in in vivo long-term imaging of mouse tumors with a high signal-to-noise ratio. Thus, the present work is anticipated to shed light on the preparation of a library of AIE-active functionalized acrylonitriles with intriguing properties for biomedical applications.

Planar donor and acceptor (D–A) conjugated structures are generally believed to be the standard for architecting highly efficient photothermal theranostic agents, in order to restrict intramolecular motions in aggregates (nanoparticles). However, other channels of extra nonradiative decay may be blocked. Now this challenge is addressed by proposing an “abnormal” strategy based on molecular motion in aggregates. Molecular rotors and bulky alkyl chains are grafted to the central D–A core to lower intermolecular interaction. The enhanced molecular motion favors the formation of a dark twisted intramolecular charge transfer state, whose nonradiative decay enhances the photothermal properties. Result shows that small-molecule NIRb14 with long alkyl chains branched at the second carbon exhibits enhanced photothermal properties compared with NIRb6, with short branched chains, and much higher than NIR6, with short linear chains, and the commercial gold nanorods. Both in vitroand in vivoexperiments demonstrate that NIRb14 nanoparticles can be used as nanoagents for photoacoustic imaging-guided photothermal therapy. Moreover, charge reversal poly(β-amino ester) makes NIRb14 specifically accumulate at tumor sites. This study thus provides an excited molecular motion approach toward efficient phototheranostic agents.

Constructing artificial helical structures through hierarchical self-assembly and exploring the underlying mechanism are important, and they help gain insight from the structures, processes, and functions from the biological helices and facilitate the development of material science and nanotechnology. Herein, the two enantiomers of chiral Au(I) complexes (S)-1and (R)-1were synthesized, and they exhibited impressive spontaneous hierarchical self-assembly transitions from vesicles to helical fibers. An impressive chirality inversion and amplification was accompanied by the assembly transition, as elucidated by the results of in situand time-dependent circular dichroism spectroscopy and scanning electron microscope imaging. The two enantiomers could serve as ideal chiral templates to co-assemble with other achiral luminogens to efficiently induce the resulting co-assembly systems to show circularly polarized luminescence (CPL). Our work has provided a simple but efficient way to explore the sophisticated self-assembly process and presented a facile and effective strategy to fabricate architectures with CPL properties.

Controlling molecular assembled structures of a single luminogen through external manipulation is a general and powerful concept for designing emission-tunable materials. However, these reported powder-like compounds generally show limited emission color, high serendipitous-discovery dependence and poor mechanical properties. To overcome these limitations, we describe a simple yet powerful strategy that is adapted from methods used to control bulk commodity polymers, to modulate the molecular assembled architecture of dopant. We use luminogens with aggregation-induced emission characteristics and intrinsic blue and yellow emissions at their crystalline and amorphous states as demonstrations. When incorporating such luminogens (AIEgens) in the desired polymer matrix with tailored microstructure, white light and white circularly polarized light are generated, which are inaccessible from single and achiral AIEgen alone. The introduced strategy for realizing diverse light emission is an innovative way of developing luminogens and provides useful continuous emissive materials in the forms of macroscopic films and fibers for developing flexible devices and wearable systems.

Many highly ordered structures with smart functions are generated by self-assembly with stimuli responsiveness. Despite that electron microscopes enable us to directly observe the end products, it is hard to visualize the initial step and the kinetic stimuli-responsive behavior of self-assembly. Here, we report the design and synthesis of stereogenic amphiphiles, namely, (Z)-TPE-OEG and (E)-TPE-OEG, with aggregation-induced emission (AIE) characteristics from the hydrophobic tetraphenylethene core and thermoresponsive behavior from the hydrophilic oligoethylene glycol monomethyl ether chain. The two isomers can be easily isolated by high-performance liquid chromatography and characterized by 2D NMR spectroscopy. While (Z)-TPE-OEG self-assembles into vesicles, its (E)-cousin forms micelles in water. The initial step of their self-assembly processes can be visualized based on AIE characteristics, with a sensitivity much higher than the method based on transmittance measurement. The entrapment and release capabilities of the (Z)-stereogenic amphiphile are demonstrated by employing pyrene as a guest. The thermoresponsive behavior of the (Z)-amphiphile results in its continuous phase transition from microscopic self-assembly to macroscopic aggregation, which is successfully visualized in situby confocal laser scanning microscopy accompanied by the AIE technique. Such a kinetic process shows different stages according to the microscopic visualization, and these stages have never been monitored through roughly observing the appearance of precipitates. It is anticipated that this study can deepen the understanding of the self-assembly processes for better monitoring and controlling them in different systems.

Through‐space interaction (TSI) has been proven to play an important role in the newly emerging clusteroluminescence (CL) phenomenon. However, it is still a big challenge to manipulate the TSI at the molecular level due to the unclear relationship between the non‐conjugated structure and TSI properties. Herein, the TSI in diphenylmethane is manipulated by breaking its symmetric structures and changing the isolated subunits. Finally, the CL wavelength and efficiency of diphenylmethane are successfully regulated at the aggregate state. This work not only demonstrates the through‐space interaction (TSI) in diphenylmethane (DPM) but also provides new strategies for the manipulation of TSI and clusteroluminescence in DPM derivatives by breaking the symmetric structures and changing the isolated subunits.

Polymers with aggregation-induced emission (AIE) characteristics have aroused tremendous interest because of their potential applications in large-area flexible display and luminescent self-assembling, and as stimuli-responsive and porous materials. However, the design of AIE-active polymers is always not as easy as that of small molecules because their properties are hard to predict. In some cases, the polymers prepared from the AIE-active monomers show the aggregation-caused quenching (ACQ) instead of AIE effect. To understand the structure–property relationship of the polymers constructed from the AIE monomers, in this paper, two pyrazine-containing AIE monomers were utilized to construct luminescent polymers by click polymerization. The photophysical property investigation indicates that the polytriazole containing tetraphenylpyrazine units is AIE-active, whereas that bearing 2,3-dicyano-5,6-diphenylpyrazine units suffers from the ACQ effect. Through systematical investigation, the cause for such difference was unveiled. Thus, this work provides a useful guidance for further design of AIE-active polymers.

In 2021, The MOE Key Laboratory of Macromolecular Synthesis and Functionalization in Zhejiang University had achieved several important results. First, a series of versatile organoboron catalysts were synthesized for ring-opening (co)polymerizations. Second, a catalyst-free polycondensation mechanism was proposed for the production of polyesters with high molecular weights. Third, a co-assembly method that can fabricate films and coatings with controllable structures and properties on various substrates was demonstrated, providing a platform for the construction of novel surface coatings. Forth, facile methods for producing high-productivity poly(propylene carbonate) and semicrystalline polyester have been discovered. And linear non-conjugated polyesters exhibiting yellow-green clusteroluminescence were developed for the first time. Fifth, a supramolecular prodrug nano-assembly strategy has been developed for reactive nitrogen species potentiated chemotherapy. Sixth, a series of tough and stiff supramolecular hydrogels with shape memory properties have been used for information encryption. Seventh, reversible fusion and fission of wet-spun graphene oxide fibers has been successfully achieved. Eighth, three non-conjugated polypeptides were synthesized and the mechanism of clusteroluminescence was studied. Ninth, a series of conducting covalent organic frameworks with high electrical conductivity and carrier mobility have been used as high-performance chemiresistor, electrocatalyst, and organic field-effect transistor. Tenth, the exploration of non-fused electron acceptors, and their photostable mechanism are exemplified for developing high-performance, low-cost and eco-friendly polymer solar cells. Finally, gel-grown long-range ordering bulk-heterojunctions has achieved improved X-ray detector performance.

Clusteroluminescence (CL) materials, as an emerging class of luminescent materials with unique photophysical properties, have received increasing attention owing to their great theoretical significance and potential for biological applications. Although much progress has been made in the design, synthesis and application of CL materials, there is still a big challenge in the emission mechanism. So far, through-space interaction has been proposed as the preliminary mechanism of the corresponding clusterization-triggered emission (CTE) effect, but a systematic theory is still needed. This review summarizes the current mechanistic understanding of CL materials including organic/inorganic small molecules, and polymers with/without isolated aromatic structures. In addition, some strategies to achieve high quantum yield, adjustable emission color, and persistent room temperature phosphorescence in CL materials are also summarized. At last, a perspective of the mechanism and application of CL materials are demonstrated, which inspire the researchers working on the development of new kinds of functional materials.

The luminogens with aggregation-induced emission (AIEgens) characteristics have been widely applied in diverse areas. However, the n-type AIEgens are to be further developed. In this paper, we designed and synthesized an n-type multifunctional AIEgen of tetraphenylethene-substituted 3,4,5-triphenyl-4H-1,2,4-triazole (BTPE-TAZ). This AIEgen can serve as both light-emitting and electron-transporting layers in organic light-emitting devices. Moreover, it also exhibits the interesting optical waveguide and reversible mechanochromic luminescence properties, which are of great potential for practical applications.

The odd–even effect is a fantastic phenomenon in nature, which has been applied in diverse fields such as organic self-assembled monolayers and liquid crystals. Currently, the origin of each odd–even effect remains elusive, and all of the reported odd–even effects are related to the ground-state properties. Here, we discover an excited-state odd–even effect in the through-space interaction (TSI) of nonconjugated tetraphenylalkanes (TPAs). The TPAs with an even number of alkyl carbon atoms (C2-TPA, C4-TPA, and C6-TPA) show strong TSI, long-wavelength emission, and high QY. However, the odd ones (C1-TPA, C3-TPA, C5-TPA, and C7-TPA) are almost nonexistent with negligible QY. Systematically experimental and theoretical results reveal that the excited-state odd–even effect is synthetically determined by three factors: alkyl geometry, molecular movability, and intermolecular packing. Moreover, these flexible luminescent TPAs possess tremendous advantages in fluorescent information encryptions. This work extends the odd–even effect to photophysics, demonstrating its substantial importance and universality in nature.

In 2022, The MOE Key Laboratory of Macromolecular Synthesis and Functionalization in Zhejiang University had achieved several important results. Firstly, a series of well-defined dinuclear organoboron catalysts were developed to precisely control the enchainment of ether and carbonate segments during the copolymerization of CO2and epoxides. Second, polyester had been synthesized through cationic copolymerization of cyclic anhydride. Third, ring-opening polymerization of carbon dioxide based valerolactone had been achieved, revealing the prospect of 3-ethylidene-6-vinyltetrahydro-2H-pyran-2-one (EVL) in utilizing CO2and synthesizing functional polymers. Fourth, machine learning methods have been applied to biomaterial research, enabling high-throughput screening of functional biomaterial surfaces for implantable devices, and searching for potent antimicrobial peptides in whole combinatorial peptide libraries. Fifth, methods of characterization of biomacromolecule RNA transcription and manipulation of nucleoside modification were developed. Sixth, artificial enzymes-armed Bifidobacterium Longum probiotics were established to tune down gut inflammation. Seventh, three-dimensional (3D) printing technologies were used to engineer tough supramolecular hydrogels. Eighth, hydroplastic foaming graphene frameworks for acoustic and conductive polymer composites were provided for application. Ninth, aggregate photophysics about the nature of through-space interactions (TSIs) and manipulating their strength in small molecules with non-conjugated structure had been elucidated. Tenth, the forming mechanism of a newfound nested texture in poly(L-lactic acid) (PLLA) spherulitic films had been revealed. Finally, the isotropically dyeing mechanism of KDP single crystals grown from hydrogels have been explored. The related works are reviewed in this paper.