Hierarchical Assembly of Coordination Macromolecules with Atypical Geometries: Gd₄₄Co₂₈ Crown and Gd₉₅Co₆₀ Cage

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(16)

Published: Feb. 11, 2022

The discovered giant clusters are always highly symmetric owing to the spontaneous assembly of one or two basic units. Herein we report Gd44 Co28 crown and Gd95 Co60 cage, formulated as [Gd44 (IDA)20 (OH)72 (CO3 )12 (OAc)28 (H2 O)64 ]⋅(ClO4 )24 [Na4 (IDA)40 (OH)150 )40 (OAc)58 O)164 ] ⋅ (ClO4 )41 IDA=iminodiacetic acid), respectively, by providing a library containing multiple low-nuclearity heart-like units crown-like tetramer found in both compounds indicate unprecedented levels, leading an atypical geometry characteristic compared directly assembled regular These not only significantly increase size Ln-Co but also exhibit enhanced magnetic entropy change at ultra-low temperatures. This work provided effective way fabricate cluster with complexity simultaneously.

Language: Английский

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Circularly polarized luminescence of lanthanide complexes: From isolated individuals, discrete oligomers, to hierarchical assemblies

InfoMat, Journal Year: 2022, Volume and Issue: 5(3)

Published: Dec. 26, 2022

Abstract Circularly polarized luminescence (CPL) is the emission featured spatial orientation equivalent to circular dichroism. Owning unique magnetic dipole‐allowed but electric‐dipole‐forbidden 4 f → transitions, chiral lanthanide complexes have been recognized as ideal candidates achieve unprecedented dissymmetry factor ( g lum ). Their inherent transition can be partly allowed, through rational design of coordination ligands lower surrounding symmetry, further endowing them with relatively high quantum yields (QYs). Moreover, blossom supramolecular chemistry in allows for construction discrete oligomers and hierarchical assemblies, rendering enhanced chiroptical activities. Here, we deploy this review by summarizing recent advances properties complexes, spanning multiple scales from isolated mononuclear individuals, polynuclear oligomers, infinite assemblies. We first introduce basic concept several important parameters assessment CPL activity. Then, coordinated different types antennas, along chirality transfer induction achiral were discussed. Next, systematical discussion on assemblies was presented. Meanwhile, state‐of‐the‐art applications CPL‐active revisited. end up conclusion prospects, involving ligands, directed hierarchically precise self‐assembly, extending complexes. image

Language: Английский

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Enantiopure FeII4L4 cages bind steroids stereoselectively

Chem, Journal Year: 2023, Volume and Issue: 9(6), P. 1549 - 1561

Published: April 12, 2023

Chiral recognition underpins many biological processes, including signaling and enzymatic transformations. Mimicry of the natural systems that include these processes can provide an understanding their fundamental mechanisms enable design synthetic capable achieving similar functions. However, reported hosts only recognize small, simple chiral guests. Here, we report self-assembly a triazatruxene trialdehyde subcomponent into enantiopure FeII4L4 cages. Their chirotopic properties well-enclosed cavities cages to complex steroids through non-covalent interactions, as elucidated by X-ray crystallography. These events occur enantioselectively diastereoselectively, spanning moderate exclusive differentiation. Notably, one cage enantiomer binds equivalent canrenone, whereas other two equivalents. Microcalorimetry experiments clarify interplay enthalpy entropy during enantioselective binding.

Language: Английский

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Stereoselective Self-Assembly of Complex Chiral Radial [5]Catenanes Using Half-Sandwich Rhodium/Iridium Building Blocks

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 144(5), P. 2379 - 2386

Published: Jan. 26, 2022

Herein, we have successfully achieved the stereoselective synthesis of two chiral radial [5]catenanes in a single step through self-assembly bidentate ligands containing l-alanine residues and binuclear half-sandwich organometallic rhodium(III)/iridium(III) clips. Remarkably, these exhibit complex stereochemical structures as revealed by single-crystal X-ray diffraction. The eight units their solid-state all planar chirality, interlocking between molecular macrocycles exhibits co-conformational mechanical helical chirality. This indicates that introduction point chirality enables efficient construction mechanically interlocked molecules. Furthermore, using d-alanine residues, with opposite also been obtained.

Language: Английский

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A Platinum(II)‐Based Molecular Cage with Aggregation‐Induced Emission for Enzymatic Photocyclization of Alkynylaniline

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 62(1)

Published: Nov. 7, 2022

Abstract Enzymes facilitate chemical conversions through the collective activity of aggregated components, but marriage aggregation‐induced emission (AIE) with molecular containers to emulate enzymatic conversion remains challenging. Herein, we report a new approach construct Pt II ‐based octahedral cage AIE characteristics for photocyclization alkynylaniline by restricting rotation pendant phenyl rings peripheral corner. With presence water, C−H⋅⋅⋅π interactions involving triphenylphosphine fragments resulted in aggregation cages into spherical particles and significantly enhanced luminescence. The kinetically inert Pt‐NP chelator, highly differentiated redox potentials ground excited states, efficient coordination activation platinum corner facilitated excellent catalysis alkynylaniline. kinetics advantages binding activating substrates an aqueous medium provide avenue develop mimics photosynthesis.

Language: Английский

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Stereoselective Construction of Chiral Linear [3]Catenanes and [2]Catenanes

Journal of the American Chemical Society, Journal Year: 2022, Volume and Issue: 145(1), P. 725 - 731

Published: Dec. 23, 2022

We have successfully constructed a chiral linear [3]catenane stereoselectively by coordination-driven self-assembly using ditopic monodentate ligand containing l-valine residues with binuclear half-sandwich organometallic rhodium(III) unit. Furthermore, increasing the steric hindrance of amino acid in ligand, [2]catenane was obtained, which can be regarded as factor catenane from topological viewpoint. Notably, resulting molecular catenanes all exhibit complex coconformational mechanical helical chirality and planar ascribed to point ligands. Linear [3]catenanes [2]catenanes opposite obtained ligands corresponding d-amino residues, been confirmed single-crystal X-ray diffraction, NMR, mass spectrometry, circular dichroism spectroscopy.

Language: Английский

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Anion‐Regulated Hierarchical Self‐Assembly and Chiral Induction of Metallo‐Tetrahedra

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(39)

Published: Aug. 8, 2023

Abstract The precise control over hierarchical self‐assembly of superstructures relying on the elaboration multiple noncovalent interactions between basic building blocks is both elusive and highly desirable. We herein report a terpyridine‐based metallo‐cage T with tetrahedral motif utilized it as an efficient block for controlled in response to different halide ions. Initially, superstructure adopted hexagonal close‐packed structure. By adding Cl − /Br or I , drastically highly‐tight packing graphite‐like arrangements, respectively, have been achieved. These unusual halide‐ion‐triggered structural changes resulted quite distinct intermolecular channels, which provided new insights into mechanism three‐dimensional supramolecular aggregation crystal growth based macromolecular construction. In addition, chiral induction can be realized addition anions, stereoselectively generated either PPPP ‐ MMMM ‐type enantiomers.

Language: Английский

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Chiral Self‐Sorting, Spontaneous Resolution, and Hierarchical Self‐Assembly in Metal–Organic Cages

Small, Journal Year: 2024, Volume and Issue: unknown

Published: May 6, 2024

The ability to collectively program chiral recognition and the hierarchical self-assembly of molecular supramolecular building blocks into complex higher-order superstructures is a significant goal in chemistry. Metal-organic cages are excellent model systems examine self-sorting build self-assembly. Herein, details on how limiting conformational flexibility incorporating hydrogen bonding functional groups ligands can influence metal-organic reported. urea-functionalized axially bis-pyridyl afford high-fidelity Pd

Language: Английский

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Adaptive helicity and chiral recognition in bright europium quadruple-stranded helicates induced by host-guest interaction

Cell Reports Physical Science, Journal Year: 2021, Volume and Issue: 3(1), P. 100692 - 100692

Published: Dec. 10, 2021

Chiral information transfer is crucial to design new functions like, for instance, sensing through chiroptical probes in which the input readout as a consequence of chiral recognition event. Herein, we report lanthanide quadruple-stranded helicates [Ln2L4]2− that show guest-to-host chirality transfer. As confirmed by X-ray diffraction (XRD) and density functional theory (DFT) calculations, these cages are present solution an equilibrating racemic mixture left- right-handed helicates. The adapt their helical conformation encapsulation guest enabling also straightforward enantiomeric excess determination. Asymmetric induction demonstrated circular dichroism (CD) circularly polarized luminescence (CPL), helicity inversion mechanism based on Bailar twist proposed studied DFT calculations. presented research contributes with unique combination confined cavities, adaptive chirality, peculiar luminescent properties, finding applications toward development optical selective via molecular recognition.

Language: Английский

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Guest‐Induced Transformations in Metal‐Organic Cages

European Journal of Inorganic Chemistry, Journal Year: 2021, Volume and Issue: 2021(43), P. 4425 - 4438

Published: Aug. 26, 2021

Abstract Stimuli‐responsive structural transformations are common in artificial coordination assemblies and can help expand the engineering of programmable functional materials. In particular, chemical guests have proven to act as stimuli signals inducing interconversions Metal‐Organic Cages (MOCs). addition cages, other related classes express reorganization upon binding produce new MOC constructs, many which do not form otherwise, exhibit properties functions available before transformation. This review highlights recent examples such a class guest‐induced transformations. The connection between changes host–guest interactions is examined for both neutral anionic guests, pointing out that in‐situ formed molecular cargoes may also exert conversions. Cases mixtures MOCs redistribute encapsulation complementary species featured. thus aims provide an update methodological insights into guest‐responsive enhancing their design applications.

Language: Английский

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