Pt(II)/Pd(II)‐Based Metallosupramolecular Architectures as Light Harvesting Systems and their Applications

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(18)

Published: Feb. 21, 2024

The development of artificial light-harvesting systems mimicking the natural photosynthesis method is an ever-growing field research. Numerous such as polymers, metal complexes, POFs, COFs, supramolecular frameworks etc. have been fabricated to accomplish more efficient energy transfer and storage. Among them, coordination complexes (SCCs) formed by non-covalent metal-ligand interaction, shown capacity not only undergo single multistep migration but also utilize harvested for a wide variety applications photocatalysis, tunable emissive systems, encrypted anti-counterfeiting materials, white light emitters This review sheds on behavior both 2D metallacycles 3D metallacages where design ingenuity has executed afford harvesting donor ligands well acceptors.

Language: Английский

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Nested non-covalent interactions expand the functions of supramolecular polymer networks

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: May 10, 2024

Abstract Supramolecular polymer networks contain non-covalent cross-links that enable access to broadly tunable mechanical properties and stimuli-responsive behaviors; the incorporation of multiple unique within such materials further expands their responses functionality. To date, however, design has been accomplished through discrete combinations distinct interaction types in series, limiting logic. Here we introduce concept leveraging “nested” supramolecular crosslinks, wherein two interactions exist parallel, control bulk material functions. demonstrate this concept, use polymer-linked Pd 2 L 4 metal–organic cage (polyMOC) gels form hollow junctions metal–ligand coordination can exhibit well-defined host-guest binding cavity. In these network junctions, thermodynamics affect those ultimately translating substantial guest-dependent changes could not be achieved traditional with series.

Language: Английский

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Light‐Responsive Supramolecular Liquid‐Crystalline Metallacycle for Orthogonal Multimode Photopatterning

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(4)

Published: Nov. 15, 2023

Abstract The development of multimode photopatterning systems based on supramolecular coordination complexes (SCCs) is considerably attractive in chemistry and materials science, because SCCs can serve as promising platforms for the incorporation multiple functional building blocks. Herein, we report a light‐responsive liquid‐crystalline metallacycle that constructed by coordination‐driven self‐assembly. By exploiting its fascinating liquid crystal features, bright emission properties, facile photocyclization capability, unique system with spatially‐controlled fluorescence‐resonance energy transfer (FRET) built through introduction photochromic spiropyran derivative, which led to realization first example orthogonal three‐modes, namely holography, fluorescence, photochromism.

Language: Английский

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Transformation of Type III to Type II Porous Liquids by Tuning Surface Rigidity of Rhodium(II)‐Based Metal‐Organic Polyhedra for CO₂ Cycloaddition

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(31)

Published: June 7, 2023

Abstract Porous liquids (PLs), a summation of porous hosts and bulky solvents bestowing permanent cavities, are the prominent emerging materials. Despite great efforts, exploration is still needed to develop new PL systems. Metal‐organic polyhedra (MOPs) with discrete molecular architectures can be considered as hosts; however, many them insoluble entities. Here we report transformation type III II PLs by tuning surface rigidity MOP, Rh 24 L , in ionic liquid (IL). Functionalization N ‐donor molecules on Rh−Rh axial sites ensue their solubilization IL which confer PLs. Experimental theoretical studies reveal bulkiness per cage apertures, cause dissolution well. The obtained PLs, capturing more CO 2 than neat solvent, have depicted higher catalytic activity for cycloaddition compared individual MOPs IL.

Language: Английский

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A B←N framework based on 1D dative B←N polymers for exclusive recognition and separation of benzene from its azeotrope

Chem, Journal Year: 2023, Volume and Issue: 9(12), P. 3532 - 3543

Published: Aug. 22, 2023

Language: Английский

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54 K Spin Transition Temperature Shift in a Fe₆L₄ Octahedral Cage Induced by Optimal Fitted Multiple Guests

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7811 - 7821

Published: March 7, 2024

Spin-crossover (SCO) coordination cages are at the forefront of research for their potential in crafting next-generation molecular devices. However, due to scarcity SCO hosts and own limited cavities, interplay between host multiple guests binding has remained elusive. In this contribution, we present a family pseudo-octahedral (M6L4, M = ZnII, CoII, FeII, NiII) assembled from tritopic tridentate ligand L with metal ions. The utilization FeII ion leads successful creation Fe6L4-type cage. Host–guest studies these M6L4 reveal capacity encapsulate four adamantine-based guests. Notably, spin transition temperature T1/2 Fe6L4 is dependent on encapsulated. inclusion adamantine yields an unprecedented shift 54 K, record guest-mediated date. This drastic ascribed synergistic effect coupled optimal fit within host. Through straightforward thermodynamic cycle, affinities high-spin (HS) low-spin (LS) states separated apparent constant. result indicates that LS state stronger affinity than HS state. Exploring thermodynamics host–guest complexes allows us examine cavity. study reveals can be manipulated by encapsulation guests, cage ideal candidate determining guest fit.

Language: Английский

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Anticancer agents based on metal organic cages

Coordination Chemistry Reviews, Journal Year: 2023, Volume and Issue: 500, P. 215546 - 215546

Published: Nov. 6, 2023

Language: Английский

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Size-controlled synthesis and near-infrared photothermal response of Cp* Rh-based metalla[2]catenanes and rectangular metallamacrocycles

Chinese Chemical Letters, Journal Year: 2023, Volume and Issue: 35(6), P. 109298 - 109298

Published: Nov. 13, 2023

Language: Английский

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Dynamically Cross‐linked Oligo[2]rotaxane Networks Mediated by Metal‐Coordination

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: July 19, 2024

Abstract Polyrotaxanes (PRs) have attracted significant research attention due to their unique topological structures and high degrees of conformational freedom. Herein, we take advantage an oligo[2]rotaxane construct a novel class dynamically cross‐linked rotaxane network (DCRN) mediated by metal‐coordination. The skeleton offers several distinct advantages: In addition retaining the merits traditional polymer backbones, ordered intramolecular motion [2]rotaxane motifs introduced dangling chains into network, thereby enhancing stretchability DCRN. Additionally, dissociation host–guest recognition subsequent sliding motion, along with breakage metal‐coordination interactions, represented integrated energy dissipation pathway enhance mechanical properties. Moreover, resulting DCRN demonstrated responsiveness multiple stimuli displayed exceptional self‐healing capabilities in gel state. Upon exposure PPh 3 , which induced deconstruction breaking coordinated cross‐linking points, could be recovered, showcasing good recyclability. These findings demonstrate untapped potential as develop open door extend advanced applications intelligent mechanically interlocked materials.

Language: Английский

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Solvent-Directed Hierarchical Self-Assembly of Tetraphenylpyrazine-Cholesterol with Amplified Circularly Polarized Luminescence

ACS Applied Materials & Interfaces, Journal Year: 2023, Volume and Issue: 15(34), P. 40817 - 40827

Published: Aug. 16, 2023

It is important to identify the effect of assembly and aggregation on chirality transfer energy transmission in supramolecular polymer system, since unordered insufficient promote luminescence enhancement transfer, even causing negative effect. Another key issue solvent hierarchically chiral self-assembly. Herein, we designed an AIE-core based building block, tetraphenylpyrazine-cholesterol (TPP-Chol), explore how component influences its aggregates and/or assemblies. Interestingly, hierarchical behavior was realized mixture MeOH/CHCl3 highly dependent MeOH content. During solvent-directed assembly, morphologic transformations, such as nanoribbons with a width 150 nm, twisted helical pitch 420 nanoribbon clusters, microflowers average diameter 5.5 μm, were obvious amplification for both circular dichroism (CD) circularly polarized (CPL) measurements. The TPP-Chol also demonstrated by time-dependent CD test. work points out complexity dynamic self-assembly regulated effect, which would be helpful development materials enhanced CPL performance chirality.

Language: Английский

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