Phosphine-Capped Effects Enable Full-Color Clusteroluminescence in Nonconjugated Polyesters.

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 polypeptides.

Polypeptides, as biomacromolecules, hold immense potential in various biological applications such as tissue engineering, immunomodulating agents, and target binding. Among these applications, the attention towards luminescent polypeptides has grown significantly, due to their ability to visualize biological processes effectively. In this perspective, we have compiled information on three distinct types of luminescent polypeptides: natural fluorescent proteins, luminophores-bioconjugated polypeptides, and synthesized polypeptides with clusteroluminescence. Last, we shed light on the significance and prospects of clusteroluminescent polypeptides, which are expected to emerge as crucial new-generation bioluminophores, offering high emission efficiency and tunable emission wavelengths.

How the Length of Through-Space Conjugation Influences the Clusteroluminescence of Oligo(Phenylene Methylene)s.

The length and mode of conjugation directly affect the molecular electronic structure, which has been extensively studied in through-bond conjugation (TBC) systems. Corresponding research greatly promotes the development of TBC-based luminophores. However, how the length and mode of through-space conjugation (TSC), one kind of weak interaction, influence the photophysical properties of non-conjugated luminophores remains a relatively unexplored field. Here, we unveil a non-linear relationship between TSC length and emission characteristics in non-conjugated systems, in contrast to the reported proportional correlation in TBC systems. More specifically, oligo(phenylene methylene)s (OPM[4]-OPM[7]) exhibit stronger TSC and prominent blue clusteroluminescence (CL) (≈440 nm) compared to shorter counterparts (OPM[2] and OPM[3]). OPM[6] demonstrates the highest solid-state quantum yield (40 %), emphasizing the importance of balancing flexibility and rigidity. Further theoretical calculations confirmed that CL of these oligo(phenylene methylene)s was determined by stable TSC derived from the inner rigid Diphenylmethane (DPM) segments within the oligomers instead of the outer ones. This discovery challenges previous assumptions and adds a new dimension to the understanding of TSC-based luminophores in non-conjugated systems.

Four-Membered Ring-Embedded Cycloarene Enabling Anti-Aromaticity and Ultra-Narrowband Emission.

Synthesis of fully fused π-conjugated cycloarenes embedded nonbenzenoid aromatics is challenging. In this work, the first example of four-membered ring-embedded cycloarene (MF2) was designed and synthesized in single-crystal form by macrocyclization and ring fusion strategies. For comparison, single bond-linked chiral macrocycle MS2 without two fused four-membered rings and its linear-shaped polycyclic benzenoid monomer L1 were also synthesized. The pronounced anti-aromaticity of four-membered rings significantly adjusts the electronic structures and photophysical properties of cycloarene, resulting in an enhancement of the photoluminescence quantum yield (PLQY) from 10.66% and 10.74% for L1 and MS2, respectively, to 54.05% for MF2, which is the highest PLQY among the reported cycloarenes. Notably, owing to the embedded four-membered rings that reduce structural displacements, MF2 exhibits an ultra-narrowband emission with a single-digit full-width at half-maximum (FWHM) of only 7 nm (0.038 eV), which sets a new record among all reported organic narrowband luminescent molecules, and represents the first example of ultra-narrowband emission in conventional polycyclic aromatic hydrocarbons (PAHs) devoid of heteroatoms.

Near-Infrared Emission Beyond 900†nm from Stable Radicals in Nonconjugated Poly(diphenylmethane).

Organic radicals with narrow energy gaps are highly sought-after for the production of near-infrared (NIR) fluorophores. However, the current repertoire of developed organic radicals is notably limited, facing challenges related to stability and low fluorescence efficiency. This study addresses these limitations by achieving stable radicals in nonconjugated poly(diphenylmethane) (PDPM). Notably, PDPM exhibits a well-balanced structural flexibility and rigidity, resulting in a robust intra-/inter-chain through-space conjugation (TSC). The stable radicals within PDPM, coupled with strong TSC, yield a remarkable full-spectrum emission spanning from blue to NIR beyond 900 nm. This extensive tunability is achieved through careful adjustments of concentration and excitation wavelength. The findings highlight the efficacy of polymerization in stabilizing radicals and introduce a novel approach for developing nonconjugated NIR emitters based on triphenylmethane subunits.

Excited-State Odd-Even Effect in Through-Space Interactions.

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.

Polymerization-Induced Crystallization of Dopant Molecules: An Efficient Strategy for Room-Temperature Phosphorescence of Hydrogels.

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.

Substrate-Responsive Pillar[5]arene-Based Organic Room-Temperature Phosphorescence.

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.

Applications of Polyacetylene Derivatives in Gas and Liquid Separation.

As a low energy consumption, simple operation and environmentally friendly separation method, membrane separation has attracted extensive attention. Therefore, researchers have designed and synthesized various types of separation membrane, such as metal organic framework (MOF), covalent organic framework (COF), polymer of intrinsic micro-porosity (PIM) and mixed matrix membranes. Some substituted polyacetylenes have distorted structures and formed micropores due to the existence of rigid main chains and substituted side groups, which can be applied to the field of membrane separation. This article mainly introduces the development and application of substituted polyacetylenes in gas separation and liquid separation based on membrane technology.

NIR Clusteroluminescence of Non-conjugated Phenolic Resins Enabled by Through-Space Interactions.

Clusteroluminescence (CL) and through-space interactions (TSIs) of non-conjugated molecules have drawn more attention due to their unique photophysical behaviors that are different from largely conjugated luminogens. However, achieving red and even near-infrared (NIR) emission from such systems is still challenging due to the intrinsic drawbacks of non-conjugated molecules and the lack of theories for structure-property relationships. In this work, six phenolic resins are designed and synthesized based on two molecule-engineering strategies: increasing the number of TSIs units and introducing electron-donating/-withdrawing groups. All phenolic resins are verified as luminogens with CL property (CLgens), and the first example of CLgens with NIR emission (maximum emission wavelength ≥680 nm) and high absolute quantum yield (47 %) is reported. Experiments and theoretical analysis reveal that two TSIs types, through-space locally excited state and through-space charge transfer state, play essential roles in achieving CL from these non-conjugated polymers, which could be manipulated via changing structural conformation and electron density or altering electron transition behaviors. This work not only provides an approach to manipulate TSIs and CL of non-conjugated polymers but also endows commercially available phenolic resins with high practical value as luminescence materials.

Through-Space Interaction of Tetraphenylethylene: What, Where, and How.

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.

Aliphatic Polyesters with White-Light Clusteroluminescence.

Single-molecule white-light emission (SMWLE) has many advantages in practical applications; however, the fabrication of SMWLE from nonconjugated luminescent polymers, namely, clusteroluminogens (CLgens), is still a big challenge. Herein, the first example of linear nonconjugated polyesters with SMWLE is reported. Twenty-four kinds of nonconjugated aliphatic polyesters with tunable clusteroluminescence (CL) colors and efficiency were synthesized by the copolymerization of six epoxides and four anhydrides. Experimental and calculation results prove that, at the primary structure level, the balance of structural flexibility and rigidity via adjusting the side-chain length significantly enhances the efficiency of CL without wavelength change. However, altering the chemical structures of the monomer from succinic anhydride to trans-maleic anhydride (MA), cis-MA, and citraconic anhydride (CA), secondary structures of these polyesters change from helix to straight and folding sheet accompanied by gradually red-shifted CL from 460 to 570 nm due to the increase in through-space n-π* interactions, as demonstrated by the computational and experimental results. Then, pure SMWLE with CIE coordination (0.30, 0.32) based on overlapped short-wavelength and long-wavelength CL is achieved in CA-based polyesters. This work not only provides further insights into the emission mechanism of CL but also provides a new strategy to manipulate the properties of CL by regulating the hierarchical structures of CLgens.

Copolymers of 4-Trimethylsilyl Diphenyl Acetylene and 1-Trimethylsilyl-1-Propyne: Polymer Synthesis and Luminescent Property Adjustment.

Poly(4-trimethylsilyl diphenyl acetylene) (PTMSDPA) has strong fluorescence emission, but its application is limited by the effect of aggregation-caused quenching (ACQ). Copolymerization is a commonly used method to adjust the properties of polymers. Through the copolymerization of 4-trimethylsilyl diphenyl acetylene and 1-trimethylsilyl-1-propyne (TMSP), we successfully realized the conversion of PTMSDPA from ACQ to aggregation-induced emission (AIE) and aggregation-induced emission enhancement (AEE). By controlling the monomer feeding ratio and with the increase of the content of TMSDPA inserted into the copolymer, the emission peak was red-shifted, and a series of copolymers of poly(TMSDPA-co-TMSP) that emit blue-purple to orange-red light was obtained, and the feasibility of the application in explosive detection was verified. With picric acid (PA) as a model explosive, a super-quenching process has been observed, and the quenching constant (KSV) calculated from the Stern-Volmer equation is 24,000 M-1, which means that the polymer is potentially used for explosive detection.

Pillararene-Induced Intramolecular Through-Space Charge Transfer and Single-Molecule White-Light Emission.

The fabrication of single-molecule white-light emission (SMWLE) materials has become a highly studied topic in recent years and through-space charge transfer (TSCT) is emerging as an important concept in this field. However, the preparation of ideal TSCT-based SMWLE materials is still a big challenge. Herein, we report a bifunctional pillar[5]arene (TPCN-P5-TPA) with a linear donor-spacer-acceptor structure and aggregation-induced emission (AIE) property. The bulky pillar[5]arene between the donor and acceptor induces a twisted conformation and a non-conjugated structure, resulting in intramolecular TSCT. In addition, the AIE feature and pillar[5]arene cavity endow TPCN-P5-TPA with responsiveness to viscosity and polar guests, by which the TSCT emission is triggered. The combination of blue locally-excited state emission and yellow TSCT emission of TPCN-P5-TPA generates SMWLE. Therefore, we provide a new and versatile strategy for the construction of TSCT-based SMWLE materials.

Altering Chain Flexibility of Aliphatic Polyesters for Yellow-Green Clusteroluminescence in 38 % Quantum Yield.

Preparation of non-conjugated polymers with long-wavelength emission and high quantum yield (QY) is still a huge challenge. Herein, we report the first example of linear non-conjugated polyester exhibiting yellow-green clusteroluminescence (CL) and a high QY of 38 %. We discovered that the polyester P3 with balanced flexibility and rigidity showed the longest CL wavelength and highest QY. Systematically photophysical characterization unravel the key role of ester cluster in the CL and the cluster formation via the aggregate of ester units was visualized. Moreover, P3 was demonstrated to be a highly selective, quick-responsive (ca. 1.2 min) and sensitive detector (detection limit is 0.78 µM) for irons owing to the fast disassociation of clusters by irons. This work not only gains further mechanistic insight into CL but also provides a new strategy to design high-efficiency and long-wavelength CL, meanwhile, enlightens the glorious application prospect of luminescent polyester.

A Dihydroazulene-Based Photofluorochromic AIE System for Rewritable 4D Information Encryption.

Dynamic patterns based on luminescent materials play an essential role in the digital age. However, it is still challenging to develop highly emissive photofluorochromic materials with dynamic behaviors to store information with multiple characteristics. Here, we report a series of dihydroazulene-based compounds which show typical aggregation-induced emission (AIE) effect. Moreover, the photo-switching ability of the dihydroazulene units, undergoing light-induced ring-opening, enables photofluorochromic properties. The photofluorochromism also shows quantitively described responses to time and temperature via a reverse ring-closing process. Ultimately, a rewritable 4D information system, embedded with a quick response code, dot matrix with microstructures, color matrix of fluorescence, and time/temperature-dependent intensity change, is established with dynamic patterns. This work not only develops a dynamic AIE skeleton with photofluorochromic properties but also provides a new strategy for information encryption and cybernetics.

Sulfur Conversion to Multifunctional Poly(O-thiocarbamate)s through Multicomponent Polymerizations of Sulfur, Diols, and Diisocyanides.

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.

How to Manipulate Through-Space Conjugation and Clusteroluminescence of Simple AIEgens with Isolated Phenyl Rings.

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.

Visualization and Manipulation of Solid-State Molecular Motions in Cocrystallization Processes.

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.

An Air-Stable Organic Radical from a Controllable Photoinduced Domino Reaction of a Hexa-aryl Substituted Anthracene.

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.