Circularly Polarized Room‐Temperature Phosphorescence and Encapsulation Engineering for MOF‐Based Fluorescent/Phosphorescent White Light‐Emitting Devices

Advanced Optical Materials, Journal Year: 2020, Volume and Issue: 8(13)

Published: May 4, 2020

Abstract Optical materials with circularly polarized luminescence and room temperature phosphorescence currently attract great attention owing to their unique optoelectronic properties. Herein, via the coordination‐induced assembly strategy, a homochiral metal–organic framework (MOF) 1 high stability porosity is successfully synthesized by using achiral triphenylamine‐based molecule as building block. Remarkably, MOF shows at simultaneously, also excellent anisotropic optical Furthermore, can serve nanocontainer construct dye‐encapsulated host–guest systems. Importantly, multicolor emissions including white‐light emission be achieved. The corresponding color rendering index correlated values of light emitting device are 73 5541 K, when dye‐loaded 1⊃RhB 10 (CIE: 0.33, 0.33) single‐phase white light‐emitting phosphor. This study first reports based on without precious metals under ambient conditions, time for phosphorescent porosity. These results will open up new pathway design porous chiroptical materials.

Language: Английский

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Beyond Chiral Organic (p-Block) Chromophores for Circularly Polarized Luminescence: The Success of d-Block and f-Block Chiral Complexes

Frontiers in Chemistry, Journal Year: 2020, Volume and Issue: 8

Published: July 28, 2020

Chiral molecules are essential for the development of advanced technological applications in spintronic and photonic. The best systems should produce large Circularly Polarized Luminescence (CPL) as estimated by their dissymmetry factor (glum), which can reach maximum values -2 ≤ glum 2 when either pure right- or left-handed polarized light is emitted after standard excitation. For matching this requirement, theoretical considerations indicate that optical transitions with magnetic weak electric transition dipole moments represent holy grail CPL. Because detrimental strong allowed transitions, popular chiral emissive organic display generally moderate factors (10-5 10-3). However, recent efforts field show be significantly enhanced activators part supramolecular assemblies liquid crystalline materials. At other extreme, EuIII SmIII based complexes, possess intra-shell parity forbidden electric, but have yielded largest reported so far ~ 1.38. Consequently, 4f-based metal complexes CPL currently candidates potential applications. They however suffer from need highly samples considerable production costs. In context, earth-abundant cheap d-block benefit a renewed interest according signal optimized despite larger covalency displayed cations compared 4f-block analogues. This essay thus aims at providing minimum overview aspects rationalizing circularly luminescence exploitation design Beyond corroboration f-f ideal generating factors, special attention focused on attempts to use CrIII up 0.2. could pave way replacing high cost rare-earth metals

Language: Английский

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Visible Light Induced Rhodium(I)‐Catalyzed C−H Borylation

Angewandte Chemie International Edition, Journal Year: 2019, Volume and Issue: 58(43), P. 15244 - 15248

Published: Aug. 1, 2019

An efficient visible light induced rhodium(I)-catalyzed regioselective borylation of aromatic C-H bonds is reported. The photocatalytic system based on a single NHC-RhI complex capable both harvesting and enabling the bond breaking/forming at room temperature. chelating nature NHC-carboxylate ligand was critical to ensure stability RhI provide excellent activities. Experimental mechanistic studies evidenced photooxidative ortho addition upon irradiation with blue LEDs, leading cyclometalated RhIII -hydride intermediate.

Language: Английский

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Coordination Versatility of NHC-metal Topologies in Asymmetric Catalysis: Synthetic Insights and Recent Trends

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 478, P. 214922 - 214922

Published: Dec. 15, 2022

Language: Английский

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Recent Advances in Catalysis Involving Bidentate N-Heterocyclic Carbene Ligands

Molecules, Journal Year: 2021, Volume and Issue: 27(1), P. 95 - 95

Published: Dec. 24, 2021

Since the discovery of persistent carbenes by isolation 1,3-di-l-adamantylimidazol-2-ylidene Arduengo and coworkers, we witnessed a fast growth in design applications this class ligands their metal complexes. Modular synthesis ease electronic steric adjustability made sigma donors highly popular among chemists. While nature metal-carbon bond transition complexes bearing N-heterocyclic (NHCs) is predominantly considered to be neutral or dative bonds, strength dependent on energy match between highest occupied molecular orbital (HOMO) NHC ligand that ion. Because versatility, coordination chemistry with was explored almost all ions. Other than metals, NHCs are also capable establishing chemical main group elements. The advances catalytic linked second tether discussed. For clarity, more frequently targeted reactions first. Carbon–carbon coupling reactions, transfer hydrogenation alkenes carbonyl compounds, ketone hydrosilylation, chiral catalysis reactions. Areas where efficacy based systems were lesser extent include CO2 reduction, C-H borylation, alkyl amination, hydroamination Furthermore, covered.

Language: Английский

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Antimicrobial Properties of Amino-Acid-Derived N-Heterocyclic Carbene Silver Complexes

Pharmaceutics, Journal Year: 2022, Volume and Issue: 14(4), P. 748 - 748

Published: March 30, 2022

Complexes {Ag[NHCMes,R]}n (R = H, 2a; Me, 2b and 2b'; iPr, 2c; iBu, 2d), were prepared by treatment of imidazolium precursor compounds [ImMes,R] (2-(3-mesityl-1H-imidazol-3-ium-1-yl)acetate, 1a, (S)-2-alkyl(3-mesityl-1H-imidazol-3-ium-1-yl)acetate, 1b-d, (R)-2-methyl(3-mesityl-1H-imidazol-3-ium-1-yl)acetate, 1b', with Ag2O under appropriate conditions. They characterised analytical, spectroscopic (IR, 1H, 13C NMR polarimetry), X-ray methods (2a). In the solid state, 2a is a one-dimensional coordination polymer, in which silver(I) cation bonded to carbene ligand carboxylate group symmetry-related Ag[NHCMes,H] moiety. The environment silver centre well described DFT study dimeric model {Ag[NHCMes,H]}2. antimicrobial properties these complexes evaluated versus Gram-negative bacteria E. coli P. aeruginosa. From observed MIC MBC values (minimal inhibitory concentration minimal bactericidal concentration, respectively), complex 2b' showed best (eutomer), significantly better than those its enantiomeric derivative (distomer). Additionally, analysis 2a-d reveal clear structure-antimicrobial effect relationship. Antimicrobial activity decreases when steric R alkyl increase.

Language: Английский

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Enantiopure, luminescent, cyclometalated Ir(iii) complexes with N-heterocyclic carbene-naphthalimide chromophore: design, vibrational circular dichroism and TD-DFT calculations

Dalton Transactions, Journal Year: 2022, Volume and Issue: 51(7), P. 2750 - 2759

Published: Jan. 1, 2022

A series of chiral cyclometalated iridium complexes the type [Ir(C^N)2(C^C:)], {(C^N) = ppy (2); dfppy (3)} featuring a naphthalimide N-heterocyclic carbene ligand (C^C:) (Naphthalimide-NHC) are described and fully characterized. The racemic rac-2 rac-3 were resolved via column chromatography techniques into their corresponding enantiopure species Δ-2, Λ-2, Δ-3, Λ-3 as confirmed by CD curves. This unique class molecules containing organic inorganic chromophores might be used platform to probe stereochemical effect on photophysical properties. Vibrational circular dichroism (VCD) was an important tool assign successfully stereochemistry enantiomers. TD-DFT calculations also advanced support experimental studies rationalize observed results.

Language: Английский

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Dynamic Ir(III) Photosensors for the Major Human Drug-Metabolizing Enzyme Cytochrome P450 3A4

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(7), P. 3305 - 3320

Published: Feb. 9, 2023

Probing the activity of cytochrome P450 3A4 (CYP3A4) is critical for monitoring metabolism pharmaceuticals and identifying drug–drug interactions. A library Ir(III) probes that detect occupancy CYP3A4 active site were synthesized characterized. These show selectivity inhibition, low cellular toxicity, Kd values as 9 nM, are highly emissive with lifetimes up to 3.8 μs in cell growth media under aerobic conditions. long emission allow time-resolved gating distinguish probe from background autofluorescence live cells. X-ray crystallographic analysis revealed structure–activity relationships preference or indifference toward resolved stereoisomers. Ir(III)-based quenching upon binding, then increases following displacement inhibitors substrates. Importantly, lead inhibit at concentrations 300 nM CYP3A4-overexpressing HepG2 cells accurately mimic human hepatic drug metabolism. Thus, agents promise novel chemical tools a high-throughput manner gain insight into

Language: Английский

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Recent developments in amino acid-derived imidazole-, imidazolium- and N-heterocyclic carbene-carboxylate complexes

Inorganica Chimica Acta, Journal Year: 2023, Volume and Issue: 557, P. 121717 - 121717

Published: Aug. 11, 2023

Compounds based on imidazole or imidazolium moieties are excellent building blocks for the preparation of a plethora ligand precursors. The introduction chirality in these compounds is relatively easy through Debus-Radziszewski reaction, which chiral pools natural non-natural amino acids. Using this synthetic route, enantiopure imidazole-carboxylate, imidazolium-carboxylate, and imidazolium-dicarboxylate precursors can be prepared, from N-heterocyclic carbenes (NHC) with one two carboxylate groups also obtained. This review personal account that summarizes our recent results regarding use all as ligands coordinated to several transition metals (Cu, Zn, Ag Mo). structural features new synthesized coordination polymers novel bonding modes will described, capabilities rationalized basis theoretical calculations. efficiency homochiral inductors asymmetric catalysis discussed. Finally, antimicrobial antitumoral activities imidazolium- NHC- silver complexes found chirality-activity structure-activity relationships highlighted.

Language: Английский

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Visible Light Induced Rhodium(I)‐Catalyzed C−H Borylation

Angewandte Chemie, Journal Year: 2019, Volume and Issue: 131(43), P. 15388 - 15392

Published: Aug. 1, 2019

Abstract An efficient visible light induced rhodium(I)‐catalyzed regioselective borylation of aromatic C−H bonds is reported. The photocatalytic system based on a single NHC−Rh I complex capable both harvesting and enabling the bond breaking/forming at room temperature. chelating nature NHC‐carboxylate ligand was critical to ensure stability Rh provide excellent activities. Experimental mechanistic studies evidenced photooxidative ortho addition upon irradiation with blue LEDs, leading cyclometalated III ‐hydride intermediate.

Language: Английский

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