Macroscopic Helical Assembly of One-Dimensional Coordination Polymers: Helicity Inversion Triggered by Solvent Isomerism

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(44), С. 23948 - 23962

Опубликована: Окт. 27, 2023

Assembling macroscopic helices with controllable chirality and understanding their formation mechanism are highly desirable but challenging tasks for artificial systems, especially coordination polymers. Here, we utilize solvents as an effective tool to induce the of chiral polymers (CPs) manipulate helical sense. We chose Ni/R-,S-BrpempH2 system a one-dimensional tubular structure, where R-,S-BrpempH2 stands R-,S-(1-(4-bromophenyl)ethylaminomethylphosphonic acid). The morphology self-assemblies can be controlled by varying cosolvent in water, resulting twisted ribbons R-,S-Ni(Brpemp)(H2O)·H2O (R-,S-2T) pure H2O; needle-like crystals R-,S-Ni(Brpemp)(H2O)2·1/3CH3CN (R-,S-1C) 20 vol % CH3CN/H2O; nanofibers (R-,S-3F) 20–40 methanol/H2O or ethanol/H2O; superhelices (R-,S-4H 5H) 40 propanol/H2O. Interestingly, helicity superhelix using propanol isomer water. For Ni/R-BrpempH2 system, left-handed R-4H(M) was obtained NPA/H2O, while right-handed R-5H(P) isolated IPA/H2O. These results were rationalized theoretical calculations. Adsorption studies revealed recognition behavior these compounds. This work may contribute development CPs interesting functionalities.

Язык: Английский

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Copper(I) complexes with planar chirality realize efficient circularly polarized electroluminescence

Science China Chemistry, Год журнала: 2023, Номер 66(8), С. 2274 - 2282

Опубликована: Июль 10, 2023

Язык: Английский

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Boost the Circularly Polarized Phosphorescence of Chiral Organometallic Platinum Complexes by Hierarchical Assembly into Fibrillar Networks

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(25)

Опубликована: Апрель 10, 2024

Abstract Circularly polarized luminescence (CPL)‐active molecular materials have drawn increasing attention due to their promising applications for next‐generation display and optoelectronic technologies. Currently, it is challenging obtain CPL with both large dissymmetry factor ( g lum ) high quantum yield Φ ). A pair of enantiomeric N C‐type Pt(II) complexes L/D )‐ 1 modified chiral Leucine methyl ester are presented herein. Though the solutions these CPL‐inactive, spin‐coated thin films exhibit giantly‐amplified circularly phosphorescences | 0.53 at 560 nm air ~50 %, as well appealing circular dichroism (CD) signals maximum absorption abs 0.37–0.43 480 nm. This superior performance benefits from hierarchical formation crystalline fibrillar networks upon spin coating. Comparative studies another 2 a symmetric C coordination mode suggest that asymmetric favorable efficient exciton delocalization amplify performance. Optical in CPL‐contrast imaging inducing CP light generation achiral emitters common light‐emitting diode lamps been successfully realized.

Язык: Английский

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A Multiple Circularly Polarized Luminescence Regulation Platform Driven by Acid, Base, and Primary Amines

Advanced Optical Materials, Год журнала: 2024, Номер 12(19)

Опубликована: Апрель 30, 2024

Abstract Functional materials that exhibit circularly polarized luminescence (CPL) have shown immense potential in applications such as 3D optical displays and advanced information encryption. However, facile efficient regulation of the multiple emission properties chiral systems has remained a challenge due to scarcity suitable complexity systems. Herein, CPL platform is fabricated by helical co‐assembly an aldehyde‐functionalized fluorane dye (Rhodol‐CHO, 6′‐(diethylamino)‐3′‐hydroxy‐3‐oxo‐3H‐spiro[isobenzofuran‐1,9′‐xanthene]‐4′‐carbaldehyde) liquid crystals, which can efficiently combine stimuli‐responsive characteristics high activity. By introducing acid, base, compounds containing primary amino (─NH 2 ) groups, property system be easily modified. The obtained apparent asymmetry, with g lum values reaching 0.54–0.75). Further, these modules are successfully applied multi‐mode encryption, highlighting their practical utility. Therefore, this study presents novel strategy for developing diverse behaviors based on simple‐designed platform, advancing further materials.

Язык: Английский

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Organoplatinum(II) Cruciform: A Versatile Building Block to Fabricate 2D Microcrystals with Full‐Color and White Phosphorescence and Anisotropic Photon Transport

Angewandte Chemie International Edition, Год журнала: 2022, Номер 61(11)

Опубликована: Янв. 12, 2022

Conventional square-planar platinum complexes typically form one-dimensional assemblies as a result of unidirectional metallophilic and/or π⋅⋅⋅π intermolecular interactions. Organoplatinum(II) with cruciform shape are presented herein to construct two-dimensional (2D) microcrystals full-color and white phosphorescence. These 2D crystals show unique monocomponent stacking, from either the cyclometalating or noncyclometalating ligand, bicomponent alternate stacking both ligands along different facet directions. Anisotropic tri-directional waveguiding is further implemented on single hexagonal microcrystal. results demonstrate great capability organoplatinum(II) general platform fabricate phosphorescent micro-/nanocrystals for advanced photonic applications.

Язык: Английский

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Circularly polarized luminescence from helical N,O-boron-chelated dipyrromethene (BODIPY) derivatives

Chemical Communications, Год журнала: 2022, Номер 58(23), С. 3807 - 3810

Опубликована: Янв. 1, 2022

We report N,O-boron-chelated dipyrromethene derivatives exhibiting circularly polarized luminescence (CPL) in the red/near-infrared region, both solution and aggregated state. The CPL is originated from helical chirality through intramolecular substitution of fluorine by an alkenolic substituent. self-assembly fluorophores significantly enhances |glum| values 10-4 to 10-2.

Язык: Английский

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Enhancing Circularly Polarized Phosphorescence via Integrated Top‐Down and Bottom‐Up Approach

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(41)

Опубликована: Авг. 22, 2023

In the dynamic domain of chiroptical technologies, it is imperative to engineer emitters endowed with circularly polarized luminescence (CPL) properties. This research demonstrates an advancement by employing a combined top-down and bottom-up strategy for simultaneous amplification photoluminescence quantum yield (Φ) dissymmetry factor (glum ). Square-planar Pt(II) complexes form helical assemblies, driven torsional strain induced bis(nonyl) chains. Integration chiral anions leads these assemblies prefer distinct sense. arrangement activates metal-metal-to-ligand charge transfer (MMLCT) transition that CPL-active, Φ |glum | observing upswing contingent on number aryl substituents in anions. Utilizing soft-lithographic micromolding capillaries technique, we could fabricate exquisitely-ordered, one-dimensional co-assemblies achieve metrics 0.32 0.13. Finally, our spectroscopic elucidates underlying mechanism dual amplification, making significant stride CPL-active emitters.

Язык: Английский

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Circularly Polarized Luminescence of Cyclometalated Platinum(II) Complex Excimers: Large Difference between Isomers

Inorganic Chemistry, Год журнала: 2022, Номер 61(43), С. 17154 - 17165

Опубликована: Окт. 19, 2022

A series of platinum(II) complexes bearing a chiral β-diketonato ligand and cyclometalated have been prepared. The complexes, (SP-4-3)-[Pt(ppy)(D-tac)] (ppy = 2-phenylpyridine, D-tac 3-trifluoroacetyl-(D)-camphor), (SP-4-4)-[Pt(ppy)(D-tac)], (SP-4-3)-[Pt(ppy)(D-pbc)] (D-pbc 3-perfluorobutyryl-(D)-camphor), (SP-4-4)-[Pt(ppy)(D-pbc)], their enantiomers were isolated characterized by elemental analysis, NMR, X-ray structural analysis. Photoisomerization between SP-4-3 (trans) SP-4-4 (cis) isomers was observed. Green emission due to the monomer observed in diluted solutions for all complexes. Higher quantum yields longer lifetimes green nonpolar solvents compared polar solvents. two geometrical had surprisingly different excimer formation efficiencies. For trans isomers, orange excimers at high concentrations, whereas negligible intensities cis isomers. evaluated decay time-resolved spectra. showed CPL signals, but gave pronounced signals. dissymmetry factors, g-values, (glum 0.002) enhanced over those circular dichroism (gabs 0.0002, glum/gabs 10). under oxygen very small, although an argon atmosphere strong. Therefore, color trans-isomers changed from deoxygenation.

Язык: Английский

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Strong Circularly Polarized Phosphorescence of Achiral Pt(II) Metallomesogen Induced by Using a Chiral Co‐Assembly Strategy

Advanced Optical Materials, Год журнала: 2024, Номер 12(16)

Опубликована: Фев. 21, 2024

Abstract The high planarity and heavy‐atom effect of Pt(II) metallomesogens promote their stacking in the aggregated state highly efficient phosphorescence. This makes them promising candidate materials for circularly polarized phosphorescence (CPP) triggered by using a chiral co‐assembly strategy. In this paper, nematic phase, achiral robot‐like metallomesogen ( TFPt ) is synthesized, which combines two anchored binaphthyl inducers R/S 1 or 2 to construct cholesteric liquid crystal (N*‐LC) co‐assemblies R / S 1) n ‐(TFPt) 1‐n 2) via intermolecular interactions. resultant N*‐LC 0.03 0.97 exhibit strongest CPP emission with dissymmetry factors g em up 0.18 0.27, respectively, stemming from formation regular helical nanofibers on spin‐coated films process after thermal annealing at 165 °C.

Язык: Английский

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Aggregation-induced circularly polarized phosphorescence of Pt(ii) complexes with an axially chiral BINOL ligand

Chemical Communications, Год журнала: 2023, Номер 59(27), С. 4004 - 4007

Опубликована: Янв. 1, 2023

A pair of chiral Pt(II) complexes coordinated by simple BINOL and bipyridine ligands displaying aggregation-induced phosphorescence circularly polarized luminescence were characterized X-ray crystallography absorption emission spectroscopies. The the powder sample was reddish whereas thin film dispersed in PMMA (fPf = 1 wt%) exhibited a white emission.

Язык: Английский

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