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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Heteromeric Completive Self-Sorting in Coordination Cage Systems

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(10), P. 6905 - 6911

Published: Feb. 29, 2024

Heteroleptic coordination cages, nonstatistically assembled from a set of matching ligands, can be obtained by mixing individual components or via cage-to-cage transformations homoleptic precursors. Based on the latter approach, we here describe new level self-sorting in cage systems, namely, 'heteromeric completive self-sorting'. Here, two heteroleptic assemblies type Pd2A2B2 and Pd2A2C2, sharing one common ligand component A but differing other, are shown to coexist solution. This reached either statistical mixture based some ligands B C or, alternatively, following first step integrative giving distinct Pd2B2C2 intermediate. While subtle enthalpic factors dictate outcome self-sorting, found that it is controllable. From unique three demonstrate transition strict forming Pd2AB2C heteromeric give Pd2A2C2 variation ratio. Cage-to-cage were followed NMR MS experiments. Single crystal X-ray structures for cages obtained, impressively highlighting versatility form π-stacked trans-figure-of-eight arrangement occupy cis-edges only single edge Pd2AB2C. study paves way toward control populations systems chemistry context with emerging features such as chemical information processing, adaptive guest selectivity, stimuli-responsive catalytic action.

Language: Английский

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Assembly of Six Types of Heteroleptic Pd₂L₄ Cages under Kinetic Control

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(51), P. 28061 - 28074

Published: Dec. 14, 2023

Heteroleptic assemblies composed of several kinds building blocks have been seen in nature. It is still unclear how natural systems design and create such complicated selectively. Past efforts on multicomponent self-assembly artificial metal-organic cages mainly focused finding a suitable combination to lead single as the thermodynamically most stable product. Here, we present another approach selectively produce Pd(II)-based self-assemblies under kinetic control based selective ligand exchanges weak Pd-L coordination bonds retaining original orientation metal centers kinetically stabilized cyclic structure local reversibility given certain areas energy landscape presence assist molecule that facilitates error correction bonds. The enabled us build all six types Pd

Language: Английский

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The codriven assembly of molecular metalla-links (613, 623) and metalla-knots (41, 31) via coordination and noncovalent interactions

Proceedings of the National Academy of Sciences, Journal Year: 2024, Volume and Issue: 121(27)

Published: June 28, 2024

Although mechanically interlocked molecules (MIMs) display unique properties and functions associated with their intricate connectivity, limited assembly strategies are available for synthesis. Herein, we presented a synergistic strategy based on coordination noncovalent interactions (π–π stacking CH⋯π interactions) to selectively synthesize molecular closed three-link chains ( 6 1 3 links), highly entangled figure-eight knots 4 knots), trefoil knot knot), Borromean ring 2 link). links can be created by the strategic of nonlinear multicurved ligands incorporating furan or phenyl group long binuclear half-sandwich organometallic Cp*Rh III (Cp* = η 5 -pentamethylcyclopentadienyl) clip. However, utilizing much shorter units union 2,6-naphthyl-containing ligand led because increased π–π between four consecutive stacked layers interactions. Weakening such resulted in knot. The universality this building was verified 1,5-naphthyl-containing ligand. Quantitative conversion simple macrocycle species accomplished adjusting concentrations monitored NMR spectroscopy electrospray ionization mass spectrometry (ESI-MS). Furthermore, increasing stiff π-conjugated area unit afforded ring, topology is topological isomer link. These artificial metalla-links metalla-knots were confirmed single-crystal X-ray diffraction, ESI-MS. results offer potent higher-order MIMs emphasize critical role that play creating sophisticated topologies.

Language: Английский

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Engineering Soluble Diketopyrrolopyrrole Chromophore Stacks from a Series of Pd(II)‐Based Ravels**

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(40)

Published: July 17, 2023

Abstract A strategy to engineer the stacking of diketopyrrolopyrrole (DPP) dyes based on non‐statistical metallosupramolecular self‐assembly is introduced. For this, DPP backbone equipped with nitrogen‐based donors that allow for different discrete assemblies be formed upon addition Pd(II), distinguished by number π‐stacked chromophores. Pd 3 L 6 three‐ring, a heteroleptic 2 L′ ravel composed two crossing DPPs (flanked carbazoles), and unprecedented self‐penetrated motifs (a triple 4 quadruple stack), were obtained systematically investigated. With increasing counts stacked chromophores, UV/Vis absorptions red‐shift emission intensities decrease, except compound , which stands out an exceptional photoluminescence quantum yield 51 %. This extraordinary open‐shell metal containing explainable intra‐assembly FRET process. The modular design synthesis soluble multi‐chromophore building blocks offers potential preparation nanodevices materials applications in sensing, photo‐redox catalysis optics.

Language: Английский

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Highly Anisotropic Pd2Lab2Lcc2 and Pd2Lab2Lcd2 Type Cages by Heteromeric Completive Self‐Sorting

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

Published: Aug. 20, 2024

Pd(II)-based low-symmetry coordination cages possessing anisotropic cavities are of great interest. The common strategies employed to achieve such utilize either more than one type symmetrical ligands (e.g., L

Language: Английский

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Ring‐Size Control and Guest‐Induced Circularly Polarized Luminescence in Heteroleptic Pd3A3B3 and Pd4A4B4 Assemblies

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(46)

Published: July 29, 2024

Two new structural motifs within the class of heteroleptic Pd

Language: Английский

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Efficient and Selective Construction of 4₁² Metalla‐links Using Weak C−H⋅⋅⋅Halogen Interactions

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(23)

Published: April 4, 2024

Through a coordination-driven self-assembly method, four

Language: Английский

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Controllable Topological Transformations of 8₁₈ Molecular Metalla‐knots by Oxidation of Thiazole‐Based Ligands

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(46)

Published: Oct. 3, 2023

By exploiting coordination-driven self-assembly, high yields of two 818 molecular metalla-knots could be obtained using a thiazole-moiety-containing asymmetric dipyridyl ligand 2-(pyridin-4-yl)-5-(pyridin-4-ylethynyl)benzo[d]thiazole (L1 ), as confirmed X-ray crystallographic analysis, electrospray ionization-time-of-flight/mass spectrometry (ESI-TOF/MS), and detailed liquid-state nuclear magnetic resonance (NMR) spectroscopy. To modulate the self-assembled structures, m-chloroperbenzoic acid (m-CPBA) was utilized to oxidize thiazole-based L1 N-thiazole-oxide-based 3-oxide (L2 which enabled selective construction corresponding tetranuclear macrocycles. Notably, topologically transformed from knots simple monocycles because alkyne bond inert toward m-CPBA, by NMR spectroscopy, ESI-TOF/MS, elemental analysis.

Language: Английский

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Non‐Templated Assembly of D_5h‐Symmetric Pd₅L₁₀ Rings by Precise Ligand Angle Adjustment

Chemistry - A European Journal, Journal Year: 2024, Volume and Issue: 30(27)

Published: March 5, 2024

Abstract We report a series of Pd(II) n L 2n coordination rings for which nuclearity is controlled by the binding angle corresponding bis‐monodentate bridging ligands. Judicious choice within family rather rigid ligands allowed first‐time to synthesize homoleptic five‐membered Pd 5 10 ring that does not require any template form. demonstrate control over size maintained both in solid‐, solution‐, and gas‐phase. Two X‐ray structures from with ideal angles (yielding perfect pentagonal ring) vs . suboptimal (resulting highly distorted structure) illustrate importance correct ligand geometry. A mathematical model estimating expected based on was derived DFT computations show ring‐strain major factor determining assembly outcome.

Language: Английский

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