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A supramolecular Cd( <scp>ii</scp> )-metallogel: an efficient semiconductive electronic device
摘要： A sonication-based strategy for the synthesis of a functional supramolecular Cd(II)-metallogel (CdA-OX) has been achieved through mixing cadmium(II) acetate dihydrate and oxalic acid dihydrate, a low molecular weight gelator (LMWG), in N,N-dimethyl formamide solvent at room temperature under atmospheric pressure. The mechanical properties of the supramolecular Cd(II)-metallogel were investigated through a rheological study. The pebble-like self-assembly hierarchical architecture of the supramolecular metallohydrogel was visualized through field emission scanning electron microscopy investigations. The electrical properties of the metallogel were thoroughly examined and indicate its semiconducting nature. Based on its conducting properties, the Cd(II)-metallogel was successfully applied to a Schottky barrier diode. Overall, this work is a novel instance of technologically challenging electronic device application of a Cd(II)-metallogel.
关键词： Schottky barrier diode,supramolecular Cd(II)-metallogel,sonication-based synthesis,electronic device,semiconducting nature
更新于2025-11-21 11:18:25
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Control of Excited-State Supramolecular Assembly Leading to Halide Photorelease
摘要： Ground- and excited-state control of halide supramolecular assembly was achieved through the preparation of a series of ester- and amide-functionalized ruthenium polypyridyl complexes in CH2Cl2. Hydrogen-bonding amide and alcohol groups on the receptor ligand were found to direct interactions with halide, while halide association with the ethyl ester groups was not observed. The various functional groups on the receptor ligands tuned the ground-state equilibrium constants over 2 orders of magnitude (1 × 10^5 to 1 × 10^7 M^?1), and the fractional contribution of each hydrogen-bond donor to the total equilibrium constant was determined. Pulsed-laser excitation of the complexes resulted in excited-state localization on the ester- or amide-functionalized ligands. In the case where the excited state was oriented toward an associated halide ion (the amide complexes), an 80 ± 10 meV Coulombic repulsion was induced that lowered the excited-state equilibrium constant (K*_eq) and resulted in halide photorelease. The rate constants for excited-state halide release (k*_21) were determined, and the values varied based on the functional groups present in the receptor ligand. Complexes with more hydrogen-bonding donors had smaller rate constants for halide photorelease. In a complex without a specific receptor ligand, the excited-state dipole was not oriented toward the associated halide, and the excited state was therefore found to have a larger equilibrium constant for halide association than the ground state.
关键词： halide supramolecular assembly,excited-state equilibrium,photorelease,hydrogen-bonding,ruthenium polypyridyl complexes
更新于2025-11-19 16:56:35
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Heterochiral Doped Supramolecular Coordination Networks for High-Performance Optoelectronics
摘要： Chiral self-sorting has great potential for constructing new complex structures and determining chirality-dependent properties in multicomponent mixtures. However, it is still of great challenge to achieve high fidelity chiral self-discrimination. Besides, the researches on the coordination polymers or metal-organic frameworks (CPs/MOFs) for micro-/nano-optoelectronics are still rare due to their low conductivity and difficulty in developing a rapid and simple scale-up synthetic method. Here, heterochiral supramolecular coordination networks (SCNs) were synthesized by the solvothermal reaction of naphthalene diimide enantiomers and cadmium iodide, using the chirality as a synthetic tuning parameter to control the morphologies. Intriguingly, heterochiral micro-/nanocrystals exhibited photochromic and photodetecting properties. Furthermore, we also developed a simple and efficient doping method to enhance the conductivity and photoresponsivity of micro-/nanocrystals using hydrazine. From experimental and theoretical studies, the mechanism was suggested as follows: the radicals in the singly occupied molecular orbital (SOMO) level of the ligands provide charge carriers that can undergo “through-space” transport between π–π stacked ligands and the electron transfer from adsorbed hydrazine to the SCNs results in reduction of energy gap, leading to increased conductivity. Our findings demonstrate a simple and powerful strategy for implementing coordination networks with redox ligands for micro-/nano-optoelectronic applications.
关键词： chiral self-discrimination,doping,micro-/nano-devices,optoelectronics,supramolecular coordination network
更新于2025-11-19 16:56:35
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Multi-stimuli Responsive Supramolecular Gels Based on a D-π-A Structural Cyanostilbene Derivative with Aggregation Induced Emission Properties
摘要： Developing multi-stimuli responsive fluorescent gel materials in a single system remains challenging. Gelator molecules with classical fluorophores suffer from aggregation-caused quenching (ACQ) effect, limiting their applications further. Herein, a novel V-shaped cyanostilbene-based molecule (BAPBIA) with aggregation induced emission (AIE) characteristics and great gelation ability was synthesized and was found to exhibit multi-stimuli responsive behaviors. Reversible gel-sol phase transitions together with emission quenching are realized in response to external stimuli including heating, light and fluoride ion. Especially, the introduction of dimethylaniline group (donor) and cyano group (acceptor) generates a D-π-A structure, further leading to an intramolecular charge transfer (ICT) effect, which enlarges the emission contrast with the variations of the distribution of charge. Thus, upon trifluoroacetic acid (TFA) triggered protonation of dimethylaniline group, not only gel-sol transition but also emission color switching (yellow-to-blue) is achieved due to the loss of the ICT effect. This work paves an easy way to construct fully reversible multi-stimuli responsive fluorescence modulation smart materials.
关键词： supramolecular gels,aggregation induced emission,multi-stimuli responsive,fluorescence switching,cyanostilbene derivative
更新于2025-11-14 15:14:40
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A Full-Spectrum Metal-Free Porphyrin Supramolecular Photocatalyst for Dual Functions of Highly Efficient Hydrogen and Oxygen Evolution
摘要： A full-spectrum (300–700 nm) responsive porphyrin supramolecular photocatalyst with a theoretical solar spectrum efficiency of 44.4% is successfully constructed. For the first time, hydrogen and oxygen evolution (40.8 and 36.1 μmol g?1 h?1) is demonstrated by a porphyrin photocatalyst without the addition of any cocatalysts. The strong oxidizing performance also presents an efficient photodegradation activity that is more than ten times higher than that of g-C3N4 for the photodegradation of phenol. The high photocatalytic reduction and oxidation activity arises from a strong built-in electric field due to molecular dipoles of electron-trapping groups and the nanocrystalline structure of the supramolecular photocatalyst. The appropriate band structure of the supramolecular photocatalyst adjusted via the highest occupied molecular orbital and lowest unoccupied molecular orbital energy levels of the porphyrin gives rise to thermodynamic driving potential for H2 and O2 evolution under visible light irradiation. Controlling the energy band structure of photocatalysts via the ordered assembly of structure-designed organic molecules could provide a novel approach for the design of organic photocatalysts in energy and environmental applications.
关键词： supramolecular photocatalysts,photocatalysis,full spectrum,dual functions,dipoles
更新于2025-09-23 15:23:52
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Controlling the Emergence and Shift Direction of Mechanochromic Luminescence Color of a Pyridine-Terminated Compound
摘要： In this study, mechanochromic luminescence was induced in a complex of mechano-inactive compounds. Dye/acid complexes containing the same p-conjugated backbones was prepared. While the luminophore showed blue and red shifts in photoluminescence spectra when combined with different acids by grinding, it exhibited slight mechanoresponsiveness itself. Also, compounds with similar molecular backbones to the dye/acid complex were synthesized to clarify the color change mechanism. The compounds showed both blue and red shifts in photoluminescence and diffuse reflectance spectra upon grinding, indicating that mechanochromic luminescence in the hydrogen-bonded complex is like its monomeric analogue and that aggregation structure plays an important role in the mechanoresponsive behavior rather than p-conjugated structure. We showed that mechanoinduced color change can be induced by imitating mechanoresponsive compounds without synthetic modification.
关键词： Luminescence,Supramolecular chemistry,Aggregation
更新于2025-09-23 15:23:52
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A photo-switchable supramolecular hyperbranched polymer with aggregation-induced emission based on host-guest interaction
摘要： In this work, we report a simple strategy by mixing a coumarin appended tetraphenylethylene derivative (TPEC) and γ-cydodextrin(γ-CD) in aqueous solution, based on the host-guest interaction between TPEC and γ-CD to construct a dual-modality supramolecular hyperbranched polymer. The host-guest interaction between γ-CD and TPEC efficiently restricted the intramolecular rotation and the non-radiative relaxation channel, minimizing energy loss, thereby resulting in the strong emission of TPEC in dilute solution. Moreover, we achieved the conversion between non-covalent supramolecular polymers and its corresponding covalent supramolecular hyperbranched polymers under the irradiation of UV light, which can be reversibly controlled through the irradiation at the wavelengths of 254 nm and 365 nm. Furthermore, both non-covalent supramolecular hyperbranched polymers and covalent supramolecular hyperbranched polymers can self-assemble into spherical structures. This methodology provides a new idea for exploring a new type of supramolecular hyperbranched polymers with aggregation-induced emission.
关键词： supramolecular polymer,reversible,host-guest interaction,photo-switchable,dual-modality
更新于2025-09-23 15:23:52
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A multi-color and white-light emissive cucurbituril/terpyridine/lanthanide supramolecular nanofiber
摘要： Multi-color and white light luminescence materials based on supramolecular assemblies are attractive because of their potential applications in advanced light-emitting material. Herein, a cucurbit[8]uril-enhanced lanthanide luminescent supramolecular assembly was constructed in a facile but efficient way using terpyridine imidozalium cations, cucurbit[8]urils and rare earth ions such as Tb3+ and Eu3+. Significantly, the resultant fibrous supramolecular assembly, with an average width of 15 nm, could emit remarkable lanthanide luminescence, which was ten times higher than the corresponding terpyridine/Ln3+ without cucurbit[8]uril. And the solid state luminescence of supramolecular assembly could be smartly and easily turned among blue, green, red and white by adjusting the molar ratios between Tb3+ and Eu3+. The enhanced white-light emission by supramolecular strategy may provide a new approach for smart and tunable solid luminescent materials.
关键词： Cucurbit[8]uril,White-light emission,Supramolecular chemistry,Host-guest interaction,Lanthanide luminescence
更新于2025-09-23 15:23:52
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Photoresponsive Circular Supramolecular Polymers: Topological Trap and Photoinduced Ring-opening Elongation
摘要： Topological features of one-dimensional macromolecular chains govern the properties and functionality of natural and synthetic polymers. To address this issue in supramolecular polymers, we have synthesized two topologically distinct supramolecular polymers with intrinsic curvature, i.e., circular and helically folded nanofibers, from azobenzene-functionalized supramolecular rosettes. When a mixture of circular and helically folded nanofibers was exposed to UV light, a selective unfolding of the latter open-ended supramolecular polymers was observed as a result of the curvature-impairing internal force produced by the trans-to-cis photoisomerization of the azobenzene. This distinct sensitivity suggests that the topological features of supramolecular polymers define their mechanical stability. Furthermore, the exposure of circular supramolecular polymers in more polar media to UV irradiation resulted in a ring-opening followed by a chain elongation, demonstrating that the circular supramolecular polymer can work as a topological kinetic trap.
关键词： topology,ring opening,azobenzene,supramolecular polymer,photoisomerization
更新于2025-09-23 15:23:52
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Divergent Terpyridine-Based Coordination for the Construction of Photoactive Supramolecular Structures
摘要： Exploring new materials to manipulate luminescent radiation and investigate the interaction of light and matter is one of the most compelling prospects of our century. Supramolecular chemistry has unraveled the opportunity to synergistically combine the chemical and optoelectronic properties of the most diverse classes of compounds. Among these, terpyridines have acted as pivotal ligand units that enable self-assembly of multicomponent chromophoric systems. In this review we therefore elucidate the metal-coordinating ability of these materials, that promote a plethora of aggregation-induced phenomena. In particular, fluorescence tuning, reversible stimuli-responsive phosphorescence enhancement and low-dimensional complexation have been demonstrated for carbon and sulfur based terpyridine oligomeric structures. Common thread of such processes is the versatile application of light as a trigger for spectroscopic investigation and output for superior optical, medical and sensing devices.
关键词： Luminescence,Terpyridine,Supramolecular chemistry,Polymers
更新于2025-09-23 15:23:52