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

InfoMat, Год журнала: 2022, Номер 5(3)

Опубликована: Дек. 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

Язык: Английский

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Homochiral Porous Metal–Organic Polyhedra with Multiple Kinds of Vertices

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(4), С. 2561 - 2571

Опубликована: Янв. 17, 2023

Metal-organic polyhedra featuring non-Archimedean/Platonic architectures with multiple kinds of vertices have aroused great attention for their fascinating structures and properties but are yet challenging to achieve. Here, we report a combinatorial strategy make such nonclassic polyhedral cages by combining kinetically labile metal ions non-planar organic linkers instead the usual only inert centers planar ligands. This facilitates synthesis an enantiopure twisted tetra(3-pyridyl)-based TADDOL (TADDOL = tetraaryl-1,3-dioxolane-4,5-dimethanol) ligand (L) capable binding Ni(II) produce regular convex cage, Ni6L8, two mixed metal/organic three rarely reported concave Ni14L8, Ni18L12, Ni24L16 or four vertices. Each has amphiphilic cavity decorated chiral dihydroxyl functionalities packs into three-dimensional structure. The enantioselective adsorption separation performances strongly dependent on pore structure features. Particularly, Ni14L8 Ni18L12 wide openings can be solid adsorbents adsorptive solid-phase extractive variety racemic spirodiols up 98% ee, whereas Ni6L8 smaller apertures cannot adsorb racemates. combination single-crystal X-ray diffraction analysis host-guest adduct GCMC simulation indicates that enantiospecific recognition capabilities originate from well-organized inner sphere as well interactions within microenvironment. work therefore provides attractive rational design cages, showing geometrically different those classic assemblies.

Язык: Английский

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Metallacages and Covalent Cages for Biological Imaging and Therapeutics

ACS Materials Letters, Год журнала: 2023, Номер 5(4), С. 1061 - 1082

Опубликована: Март 8, 2023

Due to their precise three-dimensional structures and tunable cavities, metallacages covalent cages have been widely used in various fields, such as catalysis, separation, sensing, biomedicine. As a result of the unique pattern directed synthesis modular assembly, can be modified many different ways construct stimuli-responsive for marker detection imaging biological applications. Additionally, agents drugs loaded into cavity achieve disease diagnosis treatment. This Review summarizes recent advances applications presents representative examples therapeutics. The problems future development directions are emphasized, which may provide clear guidance design application controllable diagnostic reagents.

Язык: Английский

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Recent progress in metal-organic cages for biomedical application: Highlighted research during 2018–2023

Coordination Chemistry Reviews, Год журнала: 2023, Номер 501, С. 215570 - 215570

Опубликована: Ноя. 24, 2023

Язык: Английский

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High-stability spherical lanthanide nanoclusters for magnetic resonance imaging

National Science Review, Год журнала: 2023, Номер 10(4)

Опубликована: Фев. 16, 2023

High-nuclear lanthanide clusters have shown great potential for the administration of high-dose mononuclear gadolinium chelates in magnetic resonance imaging (MRI). The development high-nuclear with excellent solubility and high stability water or solution has been challenging is very important expanding performance MRI. We used N-methylbenzimidazole-2-methanol (HL) LnCl3·6H2O to synthesize two spherical clusters, Ln32 (Ln = Ho, Ho32; Ln Gd, Gd32), which are highly stable solution. 24 ligands L- all distributed on periphery tightly wrap cluster core, ensuring that stable. Notably, Ho32 can remain when bombarded different ion source energies HRESI-MS immersed an aqueous pH values h. possible formation mechanism was proposed be Ho(III), (L)- H2O → Ho3(L)3/Ho3(L)4 Ho4(L)4/Ho4(L)5 Ho6(L)6/Ho6(L)7 Ho16(L)19 Ho28(L)15 Ho32(L)24/Ho32(L)21/Ho32(L)23. To best our knowledge, this first study assembly clusters. Spherical Gd32, a form aggregated Gd(III), exhibits longitudinal relaxation rate (1 T, r1 265.87 mM-1·s-1). More notably, compared clinically commercial material Gd-DTPA, Gd32 clearer higher-contrast T1-weighted MRI effect mice bearing 4T1 tumors. This time utilized Gd containing Gd(III) at molecular level higher contrast than traditional chelates; thus, using large doses agents avoided.

Язык: Английский

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Photonic properties and applications of multi-functional organo-lanthanide complexes: Recent advances

Journal of Rare Earths, Год журнала: 2023, Номер 42(1), С. 16 - 27

Опубликована: Фев. 8, 2023

Язык: Английский

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Ligand Chirality Transfer from Solution State to the Crystalline Self‐Assemblies in Circularly Polarized Luminescence (CPL) Active Lanthanide Systems

Advanced Science, Год журнала: 2024, Номер 11(18)

Опубликована: Март 6, 2024

Abstract The synthesis of a family chiral and enantiomerically pure pyridyl‐diamide ( pda ) ligands that upon complexation with europium [Eu(CF 3 SO ] result in complexes metal centered luminescence is reported; the sets enantiomers giving rise to both circular dichroism (CD) circularly polarized (CPL) signatures. solid‐state structures these metallosupramolecular systems are determined using X‐ray diffraction showing ligand chirality transferred from solution solid state. This optically favorable helical packing arrangement confirmed by recording CPL spectra crystalline assembly steady state enantioselective differential contrast (EDCC) Laser Scanning Confocal Microscopy (CPL‐LSCM) where two can be clearly distinguished.

Язык: 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, Год журнала: 2024, Номер 146(11), С. 7811 - 7821

Опубликована: Март 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.

Язык: Английский

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Regulation of lanthanide supramolecular nanoreactors via a bimetallic cluster cutting strategy to boost aza-Darzens reactions

Nature Communications, Год журнала: 2025, Номер 16(1)

Опубликована: Март 4, 2025

Supramolecular nanoreactor as artificial mimetic enzyme is attracting a growing interest due to fine-tuned cavity and host-guest molecular recognition. Here, we design three 3d-4f metallo-supramolecular nanocages with different sizes active sites (Zn2Er4L14, Zn4Er6L26, Zn2Er8L38) based on "bimetallic cluster cutting" strategy. Three exhibit differential catalysis for the three-component aza-Darzens reaction without another additive, only Zn2Er8L38 largest most lanthanides centers has excellent catalytic conversion monosubstituted disubstituted N-aryl aziridine products. The relationship investigations confirm that significantly outperforms Zn2Er4L14 smaller Zn4Er6L26 fewer Lewis acidic in multi-component mainly attributed synergy of inherent confinement effect multiple nanocage. strategy construction large windows may represent potential approach develop supramolecular high efficiency.

Язык: Английский

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Russian-Doll-Like Molecular Cubes

Journal of the American Chemical Society, Год журнала: 2020, Номер 143(6), С. 2537 - 2544

Опубликована: Дек. 30, 2020

Nanosized cage-within-cage compounds represent a synergistic molecular self-assembling form of three-dimensional architecture that has received particular research focus. Building multilayered ultralarge cages to simulate complicated virus capsids is believed be tough synthetic challenge. Here, we synthesize two large double-shell supramolecular by facile self-assembly presynthesized metal-organic hexatopic terpyridine ligands with metal ions. Differing from the mixture prisms formed inner tritopic ligand, redesigned bearing high geometric constraints led exclusive formation discrete structures. These unique nested are composed cubes (5.1 nm) and outer huge truncated (12.0 13.2 six bowl-shape subcages distributed on faces. The results weights 75 232 77 667 Da were among largest cage-in-cage supramolecules reported date. composition, size shape unambiguously characterized combination 1H NMR, DOSY, ESI-MS, TWIM-MS, TEM, AFM, SAXS. This work provides an interesting model for functional recognition, delivery, detection various guest molecules in field materials.

Язык: Английский

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