Concentric hollow multi-hexagonal platelets from a small molecule.

The creation of well-defined hollow two-dimensional structures from small organic molecules, particularly those with controlled widths and numbers of segments, remains a formidable challenge. Here we report the fabrication of the well-defined concentric hollow two-dimensional platelets with programmable widths and numbers of segments through constructing a concentric multiblock two-dimensional precursor followed by post-processing. The fabrication of concentric multi-hexagons two-dimensional platelets is realized by the alternative heteroepitaxial growth of two donor-acceptor molecules. Upon ultraviolet irradiation, one of the two donor-acceptor molecules can be selectively oxidized by singlet oxygen generated during the process, and the oxidized product becomes more soluble due to increased polarity. This allows for selective removal of the oxidized segments simply by solvent dissolution, yielding hollow multiblock two-dimensional structures. The hollow two-dimensional platelets can be utilized as templates to lithograph complex electrodes with precisely controlled gap sizes, thereby offering a platform for examining the optoelectronic performance of functional materials.

Light-Regulated Nucleation for Growing Highly Uniform Single-Crystalline Microrods.

We report a light-irradiation method to control the synchronous nucleation of a donor-acceptor (D-A) fluorophore for growing highly uniform single-crystalline microrods, which is in sharp contrast to the prevailing methods of restricting spontaneous nucleation and additionally adding seeds. The D-A fluorophore was observed to undergo photoinduced electron transfer to CrCl3, leading to the generation of HCl and the subsequent protonation of the D-A fluorophore. By intensifying photoirradiation or prolonging its duration, the concentration of protonated D-A fluorophores can be rapidly increased to a high supersaturation level. This results in the formation of a controlled number of nuclei in a synchronous manner, which in turn kickstart the epitaxial growth of protonated D-A fluorophores towards uniform single-crystalline microrods of controlled sizes. The light-regulated synchronous nucleation and uniform growth of microrods are a unique phenomenon that can only be achieved by specific Lewis acids, making it a novel probing method for sensitively detecting strong Lewis acids such as chromium chloride.

Living Self-Assembly of Metastable and Stable Two-Dimensional Platelets from a Single Small Molecule.

This study reports the design of a donor-acceptor (D-A) molecule with two fluorene units on each side of a benzothiadiazole moiety, which allows multiple intermolecular interactions to compete with one another so as to induce the evolution of the metastable 2D platelets to the stable 2D platelets during the self-assembly of the D-A molecule. Importantly, the living seeded self-assembly of metastable and stable 2D structures with precisely controlled sizes can be conveniently achieved using an appropriate supersaturated level of a solution of the D-A molecule as the seeded growth medium that can temporarily hold the almost-proceeding spontaneous nucleation from competing with the seeded growth. The stable 2D platelets with smaller area sizes exhibit higher sensitivity to gaseous dimethyl sulfide, illustrating that the novel living self-assembly method provides more available functional structures with controlled sizes for practical applications. The key finding of this study is that the new living methodology is separated into two independent processes: the elaborate molecular design for various crystalline structures as seeds and the application of a supersaturated solution with appropriate levels as the growth medium to grow the uniform structures with controlled sizes; this would make convenient and possible the living seeded self-assembly of rich 1D, 2D, and 3D architectures.

Uniform Colloidal Polymer Rods by Stabilizer-Assisted Liquid-Crystallization-Driven Self-Assembly.

The synthesis of anisotropic colloidal building blocks is essential for their self-assembly into hierarchical materials. Here, a highly efficient stabilizer-assisted liquid-crystallization-driven self-assembly (SA-LCDSA) strategy was developed to achieve monodisperse colloidal polymer rods. This strategy does not require the use of block copolymers, but only homopolymers or random copolymers. The resulting rods have tunable size and aspect ratios, as well as well-defined columnar liquid crystal structures. The integrated triphenylene units enable the rods to exhibit unusual photo-induced fluorescence enhancement and accompanying irradiation memory effect, which, as demonstrated, are attractive for information encryption/decryption of paper documents. In particular, unwanted document decryption during delivery can be examined by fluorescence kinetics. This SA-LCDSA-based approach can be extended to synthesize other functional particles with desired π-molecular units.

Fabrication of Two-Dimensional Platelets with Heat-Resistant Luminescence and Large Two-Photon Absorption Cross Sections via Cooperative Solution/Solid Self-Assembly.

The combination of solution self-assembly, which enables primary morphological control, and solid self-assembly, which enables the creation of novel properties, can lead to the formation of new functional materials that cannot be obtained using either technique alone. Herein, we report a cooperative solution/solid self-assembly strategy to fabricate novel two-dimensional (2D) platelets. Precursor 2D platelets with preorganized packing structure, shape, and size are formed via the living self-assembly of a donor-acceptor fluorophore and volatile coformer (i.e., propanol) in solution phase. After high-temperature annealing, propanol is released from the precursor platelets, and new continuous intermolecular hydrogen bonds are formed. The new 2D platelets formed retain the controllable morphologies originally defined by the solution phase living self-assembly but exhibit remarkable heat-resistant luminescence up to 200 °C and high two-photon absorption cross sections (i.e., >19,000 GM at 760 nm laser excitation).

Development of Binary Coassemblies for Sensitively and Selectively Detecting Gaseous Sarin.

The low sensitivity and poor selectivity of fluorescence sensors for real gaseous sarin detection greatly hinder their real-world applications. In this work, we report the development of a novel fluorophore with an active N-H vibration in the benzimidazole group for the sensitive detection of gaseous sarin. We demonstrate that the interactions between the nucleophilic fluorine atom in sarin and the electrophilic hydrogen atom in the benzimidazole group of the fluorophore can restrict the N-H vibration to yield sensitive fluorescence-enhancing responses. On the basis of this mechanism, the experimental and theoretical limits of detection for gaseous sarin can reach as low as 50 and 4.8 ppb, respectively. We further coassemble this fluorophore with another two D-A fluorophores containing different acceptor groups and use the resulting coassemblies as sensor array members to obtain access to differential combined responses to gaseous sarin compared with various interferents, including diethylchlorophosphate and acids. This two-member sensor array proves to be capable of detecting trace sarin in complex environments, demonstrating its potential applications in the real world.

Unprecedented Small Molecule-Based Uniform Two-Dimensional Platelets with Tailorable Shapes and Sizes.

Fabrication of uniform two-dimensional (2D) structures from small molecules remains a formidable challenge for living self-assembly despite its great success in producing uniform one-dimensional (1D) structures. Here, we report the construction of unprecedented uniform 2D platelets with tailorable shapes and controlled sizes by creating new nuclei from a donor-acceptor (D-A) molecule and 1-hexanol to initiate 2D living self-assembly. We demonstrate that the D-A molecule undergoes 1-hexanol-induced twisting to form continuous alternative hydrogen bonds in-between under electrostatic attraction, which in turn forms a new nucleus. This connection architecture of the new nucleus allows to simultaneously regulate the growth rate of 1 in two dimensions to generate 2D platelets of distinct shapes through simply varying the amount of 1-hexanol relative to hexane. Furthermore, the living nature of the new nucleus enables seeded growth of complex concentric multiblock 2D heteroplatelets by sequential and alternative addition of different D-A molecules. Interestingly, the resulting 2D platelets obtained by such living self-assembly exhibit enhanced photostability compared to those obtained by conventional self-assembly without the involvement of 1-hexanol.

Rapid Assessment of Meat Freshness by the Differential Sensing of Organic Sulfides Emitted during Spoilage.

In this work, we report the fabrication of a two-member fluorescence sensor array that enables the assessment of three stages (fresh, slightly spoiled, and moderately or severely spoiled) of meat spoilage. The first member of the array, which has strong chalcogen bonding and sulfur-π interactions with organic sulfides, exhibits very high sensitivity, while the second member of the array, which has weak chalcogen bonding and sulfur-π interactions with organic sulfides, exhibits lower sensitivity. On the basis of the combined fluorescence responses of the two members, three stages of meat spoilage, including fresh, slightly spoiled, and moderately or severely spoiled, can be monitored. Notably, using the volatiles collected from 5 g of meat products over a short period of time (1 min), this two-member sensor array achieves sensitive responses to the organic sulfides emitted from the meats. The capacity of this method to rapidly assess meat freshness facilitates its practical application, as illustrated by the monitoring of the freshness of chicken and pork products in the real world.

Emergent Photostability Synchronization in Coassembled Array Members for the Steady Multiple Discrimination of Explosives.

The design of sensor array members with synchronous fluorescence and photostability is crucial to the reliable performance of sensor arrays in multiple detections and their service life. Herein, a strategy is reported for achieving synchronous fluorescence and photostability on two coassemblies fabricated from carbazole-based energy donor hosts and a photostable energy acceptor. When a small number of the same energy acceptors are embedded into two carbazole-based energy donor hosts, the excitation energy of the donors can be efficiently harvested by the acceptors through long-range exciton migration and Förster resonance energy transfer (FRET) to achieve synchronous fluorescence and photostability in both coassemblies. More intriguingly, the synchronous photostability substantially improves the multiple discrimination capacity (e.g., 10 times more discriminations of TNT in two coassemblies have been achieved compared to the sensor array comprising two individual donor assemblies) and the working lifetime of the sensor array. The concept of optical synchronization (i.e., emission and photostability) of sensor array members can be extended to other sensor arrays for the steady multiple detection of certain hazardous chemicals.

Development of a Fluorophore with Enhanced Unorthodox Chalcogen Bonding for Highly Sensitive Detection of Trimethyl Arsine Vapor.

In this work, we report the design of novel fluorophores that bear three benzothiadiazole and benzoselenadiazole groups, respectively, for sensitive detection of trimethyl arsine vapor. In particular, the fluorophore with the benzoselenadiazole groups can form stronger chalcogen bonding with trimethyl arsine than the fluorophore with the benzothiadiazole groups, which in turn triggers much faster and more sensitive fluorescence responses. On the basis of this novel mechanism, fluorescence detection of trimethyl arsine vapor with rapid response (∼3 s), high sensitivity (the theoretical LOD is 0.44 ppb), and high selectivity is achieved on bundled nanofibers from the fluorophore with the benzoselenadiazole groups. Here, the new fluorescence sensor may find wide applications in health and environmental monitoring, arsenic distribution recognition in soil, and arsenic mines exploration.

Highly Photostable and Luminescent Donor-Acceptor Molecules for Ultrasensitive Detection of Sulfur Mustard.

Real-time, high signal intensity, and prolonged detection is challenging because of the rarity of fluorophores with both high photostability and luminescence efficiency. In this work, new donor-acceptor (D-A) molecules for overcoming these limitations are reported. A hybridized local and an intramolecular charge-transfer excited state is demonstrated to afford high photoluminescence efficiency of these D-A molecules in solution (≈100%). The twisted molecular structure and bulky alkyl chains effectively suppress π-π and dipole-dipole interactions, enabling high luminescence efficiency of 1 and 2 in the solid state (≈94% and 100%). Furthermore, two D-A aggregates exhibit high photostability as evidenced by 4% and 8% of the fluorescence decreasing after 6 h of continuous irradiation in air, which is in sharp contrast to ≈95% of fluorescence decreasing in a reference compound. Importantly, with these molecules, ultrasensitive detection of sulfur mustard (SM) with a record limit of 10 ppb and selective detection of SM in complex matrices are achieved.

Long-Range Exciton Migration in Coassemblies: Achieving High Photostability without Disrupting the Electron Donation of Fluorene Oligomers.

In this work, photostable coassemblies from a nonphotostable fluorene oligomer (the energy donor) and a photostable oligomer (the energy acceptor) are fabricated. Long-range exciton migration over a net distance of about 370 energy-donor molecules to energy acceptors is demonstrated in such coassemblies. The fast and long energy migration allows harvesting of the excitation energy of energy donors by embedding a small number of energy acceptors for photostability enhancement. Importantly, embedding a small number of energy acceptors in coassemblies causes a negligible negative influence on the electron donation of energy donors that are desired in practical applications. The advantages of the coassemblies fabricated, that is, high photostability without disrupting the electron donation of energy donors, are well illustrated in fluorescence detection of trace explosives where prolonged working life and improved detection capacity are achieved.

Stable organic self-assembled microwire lasers for chemical vapor sensing.

Organic microlasers hold great potentials in fabricating on-chip sensors for integrated photonic circuits due to their chemical versatility and reactivity. However, chemical vapor detection is still challenging for organic microlaser sensors, as it requires not only optical gain and self-assembly capability, but also rapid response to stimuli and long-term stability under high excitation power. In this work, a new laser dye 4,7-bis(9-octyl-7-(4-(octyloxy)phenyl)-9H-carbazol-2-yl)benzo[c][1,2,5]thiadiazole (BPCBT) is designed and synthesized, which self-assembles into microwires showing strong intramolecular charge transfer (ICT) photoluminescence with >80% quantum efficiency. It enables the lasing from BPCBT microwires under a low threshold of 16 µJ·mm-2·pulse-1 with significantly improved stability over conventional organic microlasers. The stimulated emission amplifies the fluorescence change in the BPCBT microwires under chemical vapors including various acid, acetone, and ethanol vapors, indicating high sensitivity and high selectivity of organic microlaser sensors desirable for compact sensor arrays in integrated photonics.

Universal Strategy for Improving the Sensitivity of Detecting Volatile Organic Compounds by Patterned Arrays.

The diffusion of target analytes is a determining factor for the sensitivity of a given gas sensor. Surface adsorption results in a low-concentration region near the sensor surface, producing a concentration gradient perpendicular to the surface, and drives a net flux of molecules toward solid reactive reagents on the sensor surface, that is, vertical diffusion. Here, organic semiconductor supramolecules were patterned into micromeshed arrays to integrate vertical and horizontal diffusion pathways. When used as a gas sensor, these arrays have an order of magnitude higher sensitivity than traditional film-based sensors. The sensor sensitivity ramp down with the increase in coverage density of reactive reagents, yielding two linear regions demarcated by 0.3 coverage, which are identified by the experimental results and simulations. The universal nature of template-assisted patterning allows adjustments in the composition, size, and shape of the constituent material, including nanofibers, nanoparticles, and molecules, and thus serves to improve the sensitivity of gas sensors for detecting various volatile organic compounds.

Light-Driven Crawling of Molecular Crystals by Phase-Dependent Transient Elastic Lattice Deformation.

The light-driven crawling of a molecular crystal that can form three phases, (α, ß, and γ) is presented. Laser irradiation of the molecular crystal can generate phase-dependent transient elastic lattice deformation. The resulting elastic lattice deformation that follows scanning irradiation of a laser can actuate the different phases of molecular crystal to move with different velocity and direction. Because the γ phase has a large Young's modulus (ca. 26 GPa), a force of 0.1 µN can be generated under one laser spot. The generated force is sufficient to actuate the γ-formed molecular crystals in a wide dimensional range to move longitudinally at a velocity of about 60 µm min-1 , which is two orders of magnitude faster than the α and ß phases.

Monolayer Two-dimensional Molecular Crystals for an Ultrasensitive OFET-based Chemical Sensor.

The sensitivity of conventional thin-film OFET-based sensors is limited by the diffusion of analytes through bulk films and remains the central challenge in sensing technology. Now, for the first time, an ultrasensitive (sub-ppb level) sensor is reported that exploits n-type monolayer molecular crystals (MMCs) with porous two-dimensional structures. Thanks to monolayer crystal structure of NDI3HU-DTYM2 (NDI) and controlled formation of porous structure, a world-record detection limit of NH3 (0.1 ppb) was achieved. Moreover, the MMC-OFETs also enabled direct detection of solid analytes of biological amine derivatives, such as dopamine at an extremely low concentration of 500 ppb. The remarkably improved sensing performances of MMC-OFETs opens up the possibility of engineering OFETs for ultrasensitive (bio)chemical sensing.

Sensitive Fluorescence Detection of Phthalates by Suppressing the Intramolecular Motion of Nitrophenyl Groups in Porous Crystalline Ribbons.

A novel, highly sensitive fluorescence sensor for phthalates is developed by introducing nitrophenyl groups to a trifluorene molecule that can form porous crystalline ribbons. On the basis of single-crystalline analysis and theoretical calculations, we demonstrate that phthalate molecules can diffuse into the caves of crystalline ribbons and effectively suppress the rotation of nitrophenyl groups via noncovalent interactions to enhance the emission. Because of this novel response mechanism, fluorescence detection of phthalates with high sensitivity (the limit of detection of widely used di(2-ethylhexyl) phthalate (DEHP) is 0.03 ppb) and rapid reversible turn-on responses is achieved. Sensitive detection of phthalates released from commercial polyvinyl chloride (PVC) products further illustrate the utility of such a sensor in in situ and real-world applications.

Emergent Self-Assembly Pathways to Multidimensional Hierarchical Assemblies using a Hetero-Seeding Approach.

The controlled formation of complex and functional 1-, 2-, and 3D hierarchical assemblies from molecular building blocks represents a key current challenge. Herein, we report the use of a seeded growth approach for a series of perylenediimide-based molecules (PDIs 1-4) to access otherwise inaccessible self-assembly pathways that yield complex hierarchical structures. The key to the new approach is to use hetero-seeds which possess a different composition and morphology from that of the molecular building block. For example, a nanotube seed (from PDI 3) and a microribbon seed (from PDI 4) were found to initiate different self-assembly pathways for PDI 1, which normally assembles to yield nanocoils. This led to the formation of unprecedented 3D scroll-like and scarf-like hierarchical nanostructures, respectively. Also, the hetero-seeds from PDI 3 initiate hidden self-assembly pathways of PDI 2 to generate 1D tubular heterojunctions. Significantly, this new strategy offers new opportunities to create emergent and functional hierarchical and complex structures from small molecule precursors.

Ultrasensitive Detection of Sulfur Mustard via Differential Noncovalent Interactions.

In this work, we fabricate two types of hierarchical microspheres, i.e., one coassembled from two fluorene-based oligomers (1 and 2) and one self-assembled from a fluorene-based oligomer (1), for ultrasensitive and selective detection of trace sulfur mustard (SM) vapor. On the basis of distinct fluorescence responses of 1-2 coassembled and individual 1 hierarchical microspheres that originate from differential noncovalent interactions between analytes and these sensors, SM vapor can be ultrasensitively detected (30 ppb) and easily discriminated from various sulfides and other potential interferents. Our work that utilizes differential noncovalent interactions to give sensitive and selective fluorescence response patterns represents a new detection approach for SM and other hazardous chemicals.

Turn-on Fluorescent Detection of Hydrogen Peroxide and Triacetone Triperoxide via Enhancing Interfacial Interactions of a Blended System.

In this work, we report the fabrication of a blend consisting of fluorescent 1 nanofibers and amberlyst-15 particles as a turn-on fluorescence sensor for trace TATP vapors. Fluorescence imaging and lifetime analysis reveal that the interface between 1 nanofibers and amberlyst-15 particles exhibits stronger photoluminescence than the unblended areas because of the formed strong hydrogen bonding between. Furthermore, the interfacial adhesion between 1 nanofibers and amberlyst-15 particles can be amplified by H2O2, which in turn gives rise to rapid and remarkable fluorescence enhancement. When exposed to TATP vapors, the amberlyst-15 component can rapidly decompose TATP into H2O2 that gives sensitive fluorescence enhancement responses of the blend. On the basis of this detection mechanism, fluorescence detection of TATP with rapid response (ca. 5 s) and high sensitivity (ca. 0.1 ppm) is achieved. Here, the resulting blend combines the pretreatment of TATP and detection responses and thereby simplifies the senor fabrication for the practical application.