RESUMO
Circularly polarized luminescence (CPL) is promising for applications in many fields. However, most systems involving CPL are within the visible range; near-infrared (NIR) CPL-active materials, especially those that exhibit high glum values and can be controlled spatially and temporally, are rare. Herein, dynamic NIR-CPL with a glum value of 2.5×10-2 was achieved through supramolecular coassembly and energy-transfer strategies. The chiral assemblies formed by the coassembly between adenosine triphosphate (ATP) and a pyrene derivative exhibited a red CPL signal (glum of 10-3). The further introduction of sulfo-cyanine5 resulted in a energy-transfer process, which not only led to the NIR CPL but also increased the glum value to 10-2. Temporal control of these chiral assemblies was realized by introducing alkaline phosphatase to fabricate a biomimetic enzyme-catalyzed network, allowing the dynamic NIR CPL signal to be turned on. Based on these enzyme-regulated temporally controllable dynamic CPL-active chiral assemblies, a multilevel information encryption system was further developed. This study provides a pioneering example for the construction of dynamic NIR CPL materials with the ability to perform temporal control via the supramolecular assembly strategy, which is expected to aid in the design of supramolecular complex systems that more closely resemble natural biological systems.
RESUMO
Covalent adaptable networks (CANs), leveraging the dynamic exchange of covalent bonds, emerge as a promising material to address the challenge of irreversible cross-linking in thermosetting polymers. In this work, we explore the introduction of a catalyst-free and associative C=C/C=N metathesis reaction into thermosetting polyurethanes, creating CANs with superior stability, solvent resistance, and thermal/mechanical properties. By incorporating this dynamic exchange reaction, stress-relaxation is significantly accelerated compared to imine-bond-only networks, with the rate adjustable by modifying substituents in the ortho position of the dynamic double bonds. The obtained plasticity enables recycle without altering the chemical structure or mechanical properties, and is also found to be vital for achieving shape memory functions with complex spatial structures. This metathesis reaction as a new dynamic crosslinker of polymer networks has the potential to accelerate the ongoing exploration of malleable and functional thermoset polymers.
RESUMO
Facile fabrication, low material complexity and closed-loop recycling are essential for polymer plastics to alter their linear product economy towards a cradle-to-cradle one. Covalent adaptable networks (CANs) are one way to achieve that, which intrinsically exhibit decent mechanical properties like the thermosets but could also be easily recycled like the thermoplastics. In this work, we introduce rigid ester structural motifs into dynamic poly(disulfide)s to form a series of dual polymer networks. Owning to the coherence of soft/rigid segments and the reversible sacrificial crosslinking, they exhibit tailorable mechanical properties and good resistance towards different chemicals. Their closed-loop recycling is achieved via mild solvolysis, maintaining materials' mechanical integrities. It offers a solution as a sustainable replacement for engineering plastics which are massively under production but hard to be recycled.
RESUMO
The viscosity distribution of micellar interiors from the very center to the outer surface is dramatically varied, which has been distinguished in theoretical models, yet it remains highly challenging to quantify this issue experimentally. Herein, a series of fluorophore-substituted surfactants DPAC-Fn (n = 3, 5, 7, 9, 11, 13, and 15) are developed by functionalizing the different alkyl-trimethylammonium bromides with the butterfly motion-based viscosity sensor, N,N'-diphenyl-dihydrodibenzo[a,c]phenazine (DPAC). The immersion depth of DPAC units of DPAC-Fn in cetrimonium bromide (C16TAB) micelles depends on the alkyl chain lengths n. From deep (n = 15) to shallow (n = 3), DPAC-Fn in C16TAB micelles exhibits efficient viscosity-sensitive dynamic multicolor emissions. With external standards for quantification, the viscosity distribution inside a C16TAB micelle with the size of â¼4 nm is changed seriously from high viscosity (â¼190 Pa s) in the core center to low viscosity (â¼1 Pa s) near the outer surface. This work provides a tailored approach for powerful micelle tools to explore the depth-dependent microviscosity of micellar interiors.
RESUMO
Introducing photo-responsive molecules offers an attractive approach for remote and selective control and dynamic manipulation of material properties. However, it remains highly challenging how to use a minimal amount of photo-responsive units to optically modulate materials that are inherently inert to light irradiation. Here we show the application of a light-driven rotary molecular motor as a "motorized photo-modulator" to endow a typical H-bond-based gel system with the ability to respond to light irradiation and create a reversible sol-gel transition. The key molecular design feature is the introduction of a minimal amount (2â mol %) of molecular motors into the supramolecular network as photo-switchable non-covalent crosslinkers. Advantage is taken of the subtle interplay of the large geometry change during photo-isomerization of the molecular motor guest and the dynamic nature of a supramolecular gel host system. As a result, a tiny amount of molecular motors is enough to switch the mechanical modulus of the entire supramolecular systems. This study proves the concept of designing photo-responsive materials with minimum use of non-covalent light-absorbing units.
RESUMO
Enabling dynamically tunable emissive systems offers opportunities for constructing smart materials. Clusteroluminescence, as unconventional luminescence, has attracted increasing attention in both fundamental and applied sciences. Herein, we report a supramolecular poly(disulfides) network with tunable clusteroluminescence. The reticular H-bonds synergize the rigidity and mobility of dynamic networks, and endow the resulting materials with mechanical adaptivity and robustness, simultaneously enabling efficient clusteroluminescence and phosphorescence at 77â K. Orthogonally tunable luminescence are achieved in two manners, i.e., slow backbone disulfide exchange and fast side-chain metal coordination. Further exploration of the reprocessability and chemical closed-loop recycling of intrinsic dynamic networks for sustainable materials is feasible. We foresee that the synergistic strategy of dynamic chemistry offers a novel pathway and potential opportunities for smart emissive materials.
RESUMO
Poly(1,2-dithiolane)s are a family of intrinsically recyclable polymers due to their dynamic covalent disulfide linkages. Despite the common use of thiolate-initiated anionic ring-opening polymerization (ROP) under basic condition, cationic ROP is still not exploited. Here we report that disulfide bond can act as a proton acceptor, being protonated by acids to form sulfonium cations, which can efficiently initiate the ROP of 1,2-dithiolanes and result in high-molecular-weight (over 1000â kDa) poly(disulfide)s. The reaction can be triggered by adding catalytic amounts of acids and non-coordinating anion salts, and completed in few minutes at room temperature. The acidic conditions allow the applicability for acidic monomers. Importantly, the reaction condition can be under open air without inert protection, enabling the nearly quantitative chemical recycling from bulk materials to original monomers.
RESUMO
We demonstrate that a single polycyclic π-scaffold can undergo sequential multistep excited-state structural evolution along the bent, planar, and twisted conformers, which coexist to produce intrinsic multiple fluorescence emissions in room-temperature solution. By installing a methyl or trifluoromethyl group on the ortho-site of N,N'-diphenyl-dihydrodibenzo[a,c]phenazine (DPAC), the enhanced steric effects change the fluorescence emission of DPAC from a dominant red band to well-resolved triple bands. The ultra-broadband triple emissions of ortho-substituted DPACs range from ≈350 to ≈850â nm, which is unprecedented for small fluorophores with molecular weight of <500. Ultrafast spectroscopy and theoretical calculations clearly reveal that the above dramatic changes originate from the influence of steric hindrance on the shape of excited state potential energy surface (S1 PES). Compared to the steep S1 PES of parental DPAC, the introduction of ortho-substituent is shown to make the path of structural evolution in S1 wider and flatter, so the ortho-substituted derivatives exhibit slower structural transformations from bent to planar and then to twisted forms, yielding intrinsic triple emission. The results provide the proof of concept that the bent, planar, and twisted emissive states can coexist in the same S1 PES, which greatly expand the fundamental understanding of the excited-state structural relaxation.
RESUMO
The development of a dynamic chemistry toolbox to endow materials dynamic behavior has been key to the rational design of future smart materials. The rise of supramolecular and dynamic covalent chemistry offers many approaches to the construction of dynamic polymers and materials that can adapt, respond, repair, and recycle. Within this toolbox, the building blocks based on 1,2-dithiolanes have become an important scaffold, featuring their reversible polymerization mediated by dynamic covalent disulfide bonds, which enables a unique class of dynamic materials at the intersection of supramolecular polymers and adaptable covalent networks. This Perspective aims to explore the dynamic chemistry of 1,2-dithiolanes as a versatile structural unit for the design of smart materials by summarizing the state of the art as well as providing an overview of the fundamental challenges involved in this research area and its potential future directions.
RESUMO
Photomechanical molecular crystals are promising candidates for photoactuators and can potentially be implemented as smart materials in various fields. Here, we synthesized a new molecular crystal, (E)-3-(naphthalen-1-yl)acrylaldehyde malononitrile ((E)-NAAM), that can undergo a solid-state [2 + 2] photocycloaddition reaction under visible light (≥400 nm) illumination. (E)-NAAM microcrystals containing symmetric twinned sealed cavities were prepared using a surfactant-mediated crystal seeded growth method. When exposed to light, the hollow microcrystals exhibited robust photomechanical motions, including bending and dramatic directional expansion of up to 43.1% elongation of the original crystal length before fragmentation due to the photosalient effect. The sealed cavities inside the microcrystals could store different aqueous dye solutions for approximately one month and release the solutions instantly upon light irradiation. A unique slow-fast-slow crystal elongation kinematic process was observed, suggesting significant molecular rearrangements during the illumination period, leading to an average anisotropic crystal elongation of 37.0% (±3.8%). The significant molecular structure and geometry changes accompanying the photocycloaddition reaction, which propels photochemistry to nearly 100% completion, also facilitate photomechanical crystal expansion. Our results provide a possible way to rationally design molecular structures and engineer crystal morphologies to promote more interesting photomechanical behaviors.
Assuntos
Engenharia , Luz , Cristalização/métodos , Estrutura Molecular , Fotoquímica/métodosRESUMO
To gain insights into the coupling of conformational and electronic variables, we exploited steric hindrance to modulate a polycyclic skeleton with a bent conformation in the S0 state and a twisted conformation in the S1 state under the guidance of photoexcited aromaticity reversals. Polycyclic 5,10-dihydrophenazine (DHP) adopted a bent structure in S0 but involved a bent-to-planar transformation in S1 due to the excited-state aromaticity of the 8π-electron central ring. The N,N'-locations and 1,4,6,9-sites of the DHP skeleton provided a versatile chemical handle for fine-tuning intramolecular steric hindrance. Specifically, N,N'-diphenyl-5,10-dihydrophenazine (DPP-00) and its derivatives DPP-10-DPP-22 were synthesized with different numbers of methyl groups on the 1,4,6,9-sites. X-ray crystal analyses suggested that the DHP skeletons of DPP-00-DPP-22 had more bending configurations along the N···N axis with an increase in the number of methyl groups. Following the bending-promoted interruption of π-conjugation, the absorption spectra of DPP-00-DPP-22 significantly blue-shifted from 416 to 324 nm. By contrast, the emission bands exhibited a reverse shift to longer wavelengths from 459 to 584 nm as the number of methyl substituents increased. Theoretical calculations revealed that introducing methyl groups caused the planar DHP skeleton in S1 to further twist along the N···N axis, resulting in a twisted high-strain conformation. The greater Stokes shift of the more steric-hindered structure can be attributed to the release of larger strain and aromatic stabilization energy. This research highlighted the potential promise associated with the interplay of steric effects and aromaticity reversals in a single fluorophore.
Assuntos
Elétrons , Corantes Fluorescentes , Eletrônica , Conformação MolecularRESUMO
Single-molecule conductance measurements for 9,14-diphenyl-9,14-dihydrodibenzo[a,c]phenazine (DPAC) may offer unique insight into the bent-to-planar photocycle between the ground and excited states. Herein, we employ DPAC derivative DPAC-SMe as the molecular prototype to fabricate single-molecule junctions using the scanning tunneling microscope break junction technique and explore photoconductance dependence on the excited-state structural/electronic changes. We find up to â¼200% conductance enhancement of DPAC-SMe under continuous 340 nm light irradiation than that without irradiation, while photoconductance disappears in the case where structural evolution of the DPAC-SMe is halted through macrocyclization. The in situ conductance modulation as pulsed 340 nm light irradiation is monitored in the DPAC-SMe-based junctions alone, suggesting that the photoconductance of DPAC-SMe stems from photoinduced intramolecular planarization. Theoretical calculations reveal that the photoinduced structural evolution brings about a significant redistribution of the electron cloud density, which leads to the appearance of Fano resonance, resulting in enhanced conductance through the DPAC-SMe-fabricated junctions. This work provides evidence of bent-to-planar photocycle-induced conductance differences at the single-molecule level, offering a tailored approach for tuning the charge transport characteristics of organic photoelectronic devices.
Assuntos
Eletrônica , NanotecnologiaRESUMO
Controlling dynamic stereochemistry is an important challenge, as it is not only inherent to protein structure and function but often governs supramolecular systems and self-assembly. Typically, disulfide bonds exhibit stereodivergent behavior in proteins; however, how chiral information is transmitted to disulfide bonds remains unclear. Here, we report that hydrogen bonds are essential in the control of disulfide chirality and enable stereodivergent chirality transfer. The formation of S-S···H-N hydrogen bonds in solution can drive conformational adaption to allow intramolecular chirality transfer, while the formation of C=O···H-N hydrogen bonds results in supramolecular chirality transfer to form antiparallel helically self-assembled solid-state architectures. The dependence on the structural information encoded in the homochiral amino acid building blocks reveals the remarkable dynamic stereochemical space accessible through noncovalent chirality transmission.
Assuntos
Dissulfetos , Hidrogênio , Ligação de Hidrogênio , Conformação MolecularRESUMO
Dynamic control of molecular photoluminescence offers chemical solutions to designing functional emissive materials. Although stimuli-switchable molecular luminescent systems are well established, how to encode these dynamic emissive systems with a "timing" feature, that is, time-dependent luminescent properties, remains challenging. This Concept aims to summarize the design principles of dynamic timing molecular photoluminescent systems by discussing the state-of-the-art of this topic and the shaping of fabrication strategies at both the molecular and supramolecular levels. An outlook and perspectives are given to outline the future opportunities and challenges in the rational design and potential applications of these smart emissive systems.
RESUMO
Photomechanical molecular crystals, which can directly convert light energy to mechanical energy and do mechanical work at different scales, are promising for future photoactuators. However, one of the bottlenecks in this area is how to harness the crystal shapes and sizes to achieve desired photomechanical motions and behaviors for versatile functionalities. To date, numerous techniques and strategies have been explored and developed to overcome this obstacle. In this perspective, we will summarize the progress recently made on the crystal shape and size engineering platform. Then we briefly touch on possible applications of photomechanical molecular crystals by introducing some built photoresponsive implementations. Finally, we will identify some fundamental challenges and suggestions for future applications.
RESUMO
Chemical recycling of synthetic polymers offers a solution for developing sustainable plastics and materials. Here we show that two types of dynamic covalent chemistry can be orthogonalized in a solvent-free polymer network and thus enable a chemically recyclable crosslinked material. Using a simple acylhydrazine-based 1,2-dithiolane as the starting material, the disulfide-mediated reversible polymerization and acylhydrazone-based dynamic covalent crosslinking can be combined in a one-pot solvent-free reaction, resulting in mechanically robust, tough, and processable crosslinked materials. The dynamic covalent bonds in both backbones and crosslinkers endow the network with depolymerization capability under mild conditions and, importantly, virgin-quality monomers can be recovered and separated. This proof-of-concept study show opportunities to design chemically recyclable materials based on the dynamic chemistry toolbox.
RESUMO
Developing photoresponsive circularly polarized luminescence (CPL) materials is an essential step for biosensing and biomedical applications. However, fabricating CPL assemblies rooted in the chirality amplification and transmission of the molecular building blocks, which simultaneously show photo-controllable CPL signals, remains challenging. Herein, a molecular building block containing an overcrowded-alkene core and bis-PBI (MPBI) was designed. Importantly, the enantiopure MPBI can self-assemble into well-organized nanofibers via π-π stacking interactions and enable the transmission of the intrinsic chirality, providing opposite CPL signals. The photoisomerization of MPBI induced a transformation from nanofibers to discrete nanospheres, accompanied by a gradually decreased CPL signal. The results demonstrated the development of photo-controllable CPL materials from the assembly of chiral MPBI, which provides an alternatively facile strategy to fabricate CPL-active materials and would offer opportunities for future biosensing and biomedical applications.
Assuntos
Alcenos , LuminescênciaRESUMO
Dynamic control over molecular emission, especially in a time-dependent manner, holds great promise for the development of smart luminescent materials. Here we report a series of dynamic multicolor fluorescent systems based on the time-encoded locking and unlocking of individual vibrational emissive units. The intramolecular cyclization reaction driven by adding chemical fuel acts as a chemical lock to decrease the conformational freedom of the emissive units, thus varying the fluorescence wavelength, while the resulting chemically locked state can be automatically unlocked by the hydrolysis reaction with water molecules. The dynamic molecular system can be driven by adding chemical fuels for multiple times. The emission wavelength and lifetime of the locking states can be readily controlled by elaborating the molecular structures, indicating this strategy as a robust and versatile way to modulate multi-color molecular emission in a time-encoded manner.
RESUMO
Organism-inspired hollow structures are attracting increasing interest for the construction of various bionic functional hollow materials. Next-generation self-evolution hollow materials tend to combine simple synthesis, high mechanical strength, and regular shape. In this study, we designed and synthesized a novel dry-network polythiourethane thermoset with excellent mechanical performance. The polymer film could evolve into a neat and well-organized object with a macroscopic hollow interior structure after being immersed in an aqueous NaOH solution. The self-evolution hollow structure originated from a hydrogen-bonded polymer network, which was later transformed into a network bearing both hydrogen bonds and ionic bonds. The swelling and thickness growth of this material could be controlled by the NaOH concentration and the immersion time. This unique self-evolution behavior was further utilized to produce a series of macroscopic 3D hollow-containing molds, which could be potentially applied in the production of smart materials.
Assuntos
Hidrogênio , Polímeros , Ligação de Hidrogênio , Polímeros/química , Hidróxido de Sódio , ÁguaRESUMO
The design of artificial ion channels with high activity, selectivity and gating function is challenging. Herein, we designed the light-driven motor molecule MC2, which provides new design criteria to overcome these challenges. MC2 forms a selective K+ channel through a single molecular transmembrane mechanism, and the light-driven rotary motion significantly accelerates ion transport, which endows the irradiated motor molecule with excellent cytotoxicity and cancer cell selectivity. Mechanistic studies reveal that the rotary motion of MC2 promotes K+ efflux, generates reactive oxygen species and eventually activates caspase-3-dependent apoptosis in cancer cells. Combined with the spatiotemporally controllable advantages of light, we believe this strategy can be exploited in the structural design and application of next-generation synthetic cation transporters for the treatment of cancer and other diseases.