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

---

Stereocontrolled Self-Assembly of a Helicate-Bridged Cu^I₁₂L₄ Cage That Emits Circularly Polarized Light

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(4), С. 2379 - 2386

Опубликована: Янв. 22, 2024

Control over the stereochemistry of metal–organic cages can give rise to useful functions that are entwined with chirality, such as stereoselective guest binding and chiroptical applications. Here, we report a chiral CuI12L4 pseudo-octahedral cage self-assembled from condensation triaminotriptycene, aminoquinaldine, diformylpyridine subcomponents around CuI templates. The corners this consist six head-to-tail dicopper(I) helicates whose helical chirality be controlled by addition enantiopure 1,1′-bi-2-naphthol (BINOL) during assembly process. Chiroptical nuclear magnetic resonance (NMR) studies elucidated process mechanism stereochemical information transfer BINOL Initially formed CuI(BINOL)2 thus underwent ligand exchange formation helicate cage, which determined overall stereochemistry. resulting were also shown generate circularly polarized luminescence.

Язык: Английский

---

Combining Multiple Photosensitizer Modules into One Supramolecular System for Synergetic Enhanced Photodynamic Therapy

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(11)

Опубликована: Янв. 9, 2024

Photodynamic therapy (PDT), as an emerging cancer treatment, requires the development of highly desirable photosensitizers (PSs) with integrated functional groups to achieve enhanced therapeutic efficacy. Coordination-driven self-assembly (CDSA) would provide alternative approach for combining multiple PSs synergistically. Here, we demonstrate a simple yet powerful strategy conventional chromophores (tetraphenylethylene, porphyrin, or Zn-porphyrin) pyridinium salt together through condensation reactions, followed by CDSA construct series novel metallo-supramolecular (S1-S3). The generation reactive oxygen species (ROS) is dramatically direct combination two different PSs, and further reinforced in subsequent ensembles. Among all ensembles, S2 porphyrin cores shows highest ROS efficiency, specific interactions lysosome, strong emission probing cells. Moreover, cellular living experiments confirm that has excellent PDT efficacy, biocompatibility, biosafety. As such, this study will enable more efficient potential clinical applications.

Язык: Английский

---

Circularly Polarized Luminescent π‐Conjugated Chiral Nanorings and Nanobelts

Advanced Optical Materials, Год журнала: 2024, Номер 12(18)

Опубликована: Май 20, 2024

Abstract Molecular chirality plays a pivotal role across the disciplines of chemical and physical sciences, as well holding significant implications in realms medicine technology. Chiral macrocycles have attracted recent interests synthetic chemistry, material science, supramolecular chemistry. Due to cyclic arrangements stereogenic elements or special orientations confined rigid structures, π‐conjugated chiral are expected be highly luminescent, configurationally stable, thus serve develop high‐performance chiroptical materials. Given rapid progress achieved this new area years, it is highlight concepts breakthroughs. This minireview will offer overview wide range from traditional molecules which include axially, helically, planar skeletons nanobelts with focus on structure‐function relationship between unique properties.

Язык: Английский

---

Altering the Properties of Spiropyran Switches Using Coordination Cages with Different Symmetries

Journal of the American Chemical Society, Год журнала: 2022, Номер 144(46), С. 21244 - 21254

Опубликована: Ноя. 15, 2022

Molecular confinement effects can profoundly alter the physicochemical properties of confined species. A plethora organic molecules were encapsulated within cavities supramolecular hosts, and impact cavity size polarity was widely investigated. However, extent to which guests be affected by symmetry cage─which dictates shape cavity─remains understood. Here we show that cage has a dramatic effect on equilibrium between two isomers spiropyran guests. Working with Pd-based coordination cages featuring similarly sized but differently shaped hydrophobic cavities, found highly selective stabilization isomer whose matches cage. Td-symmetric stabilized spiropyrans' colorless form rendered them photochemically inert. In contrast, D2h-symmetric favored colored isomer, while maintaining reversible photoswitching states spiropyrans. We also switching kinetics strongly depend substitution pattern scaffold. This finding used fabricate time-sensitive information storage medium tunable lifetimes encoded messages.

Язык: Английский

---

An Organo‐Palladium Host Built from a Dynamic Macrocyclic Ligand: Adaptive Self‐Assembly, Induced‐Fit Guest Binding, and Catalysis

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(42)

Опубликована: Авг. 29, 2022

Artificial hosts with rich conformational dynamics are attractive to supramolecular chemists due their adaptive guest-binding properties and enzyme-like catalytic functions. We report here the self-assembly host-guest catalysis of a new water-soluble organo-palladium host (Pd2 L2 ) built from pyridinium-bonded macrocyclic ligand (L) cis-blocked palladium corners (Pd). While direct L Pd gives rise dynamic mixture products, both neutral polyaromatic hydrocarbons an anionic polyoxometalate cluster (W10 O324- can template dominant formation Pd2 host. Guest-adaptive changes induced-fit cavity deformation have been clearly observed in crystal structures. Moreover, installation electron-rich W10 within cationic redox-active O32 ⊂Pd2 facilitates efficient selective C-H photooxidation toluene derivatives aldehyde products under mild conditions, thus representing ideal platform for green catalysis.

Язык: Английский

---

Self‐Assembly of Adaptive Chiral [1]Rotaxane for Thermo‐Rulable Circularly Polarized Luminescence

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(36)

Опубликована: Июль 16, 2022

It remains a formidable challenge to realize thermo-rulable circularly polarized luminescence (CPL). Herein, we propose new strategy by covalently "potting" the emitter into flexible chiral macrocycle as an adaptive [1]rotaxane address this issue. Different from its included analogue, potted [DS] showed conformers with tunable CPL in varied solvents. Significantly, upon controlled self-assembly, formed channel-type nanoarchitecture ([DS]A ), which exhibited extraordinary between 25-100 °C. Impressively, glum was large 0.024 at 25 °C, amplified 0.040 90 °C decrease of QY (from 92 % 80 %). By comparison, assemblies cage-type [DS]B and unpotted irreversible or unanswered thermal behaviors. The work demonstrated durable for first time provided insightful understanding effect on high-temperature switchable materials.

Язык: Английский

---

Post‐Assembly Modification of Homochiral Titanium–Organic Cages for Recognition and Separation of Molecular Isomers

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(16)

Опубликована: Фев. 21, 2023

A chiral metal-organic cage (MOC) was extended and fixed into a porous framework using post-assembly modification strategy, which made it easier to study the host-guest chemistry of solid-state MOC single-crystal diffraction technique. Anionic Ti4 L6 (L=embonate) can be used as 4-connecting crystal engineering tecton, its optical resolution achieved, thus homochiral ΔΔΔΔ- ΛΛΛΛ-[Ti4 ] cages were obtained. Accordingly, pair cage-based microporous frameworks (PTC-236(Δ) PTC-236(Λ)) easily prepared by reaction. PTC-236 has rich recognition sites provided moieties, channels high stability, affording single-crystal-to-single-crystal transformation for guest structure analyses. Thus successfully utilized separation isomeric molecules. This provides new approach orderly combination well-defined MOCs functional frameworks.

Язык: Английский

---

Luminescent terpyridine-based metallo-supramolecular systems: from design to applications

Science China Chemistry, Год журнала: 2023, Номер 66(7), С. 1940 - 1962

Опубликована: Май 22, 2023

Язык: Английский

---

Adaptive Planar Chirality of Pillar[5]arenes Invertible by n-Alkane Lengths

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(14), С. 8114 - 8121

Опубликована: Март 28, 2023

Chirality of host molecules can be induced and/or inverted by the guest molecules. However, adapting chirality hosts to length n-alkanes remains a great challenge because are neutral, achiral, and linear molecules, resulting in weak interaction with most compounds. Herein, we report system adapted n-alkane lengths, using pillar[5]arene-based macrocyclic host, S-Br, which contains five stereogenic carbons terminal bromine atoms on each rim. The electron-rich cavity S-Br could include planar-chiral isomers sensitively response lengths complexed n-alkanes. inclusion short such as n-pentane made more inclined pS-form, whereas long n-heptane pR-form favorable. difference stability was supported crystal structures theoretical calculations. Furthermore, temperature drives adaptive An middle length, n-hexane, showed dominance at higher temperature, pS-form shown lower temperature.

Язык: Английский

---