Temperature/Component‐Dependent Luminescence in Lead‐Free Hybrid Metal Halides for Temperature Sensor and Anti‐Counterfeiting

Advanced Functional Materials, Год журнала: 2024, Номер 34(34)

Опубликована: Июнь 6, 2024

Abstract Hybrid metal halides (HMHs) have emerged as a promising platform for optically functional crystalline materials, but it is extremely challenging to thoroughly elucidate the electron transition coupled additional ligand emission. Herein, discover sequences of lead‐free HMHs with distinct active cations are aimed, that is, Sb 3+ (5s 2 ) lone‐pair configuration and In (4d 10 fully‐filled configuration. (Me NH 4 M Cl 6 ·Cl = −CH 3 , Sb, In) exhibits superior temperature/component‐dependent luminescence behaviors resulting from competition between triplet‐states (T n ‐S 0 self‐trapped excitons (STEs) inorganic units singlet‐state (S 1 organic cations, which manipulated by optical activity levels [SbCl ] 3− [InCl . The bonding differences /In − in terms electronic excitation hybridization emphasized, different electron‐transition mechanisms established according PL spectra at extreme temperature 5 305 K theoretical calculations. By fine‐tuning B‐site alloying, photoluminescence quantum yield (PLQY 81.5%) stability optimized 20% alloying This research sheds light on rules governing HMHs, well exploring optical‐functional application aviation sensors access‐control systems.

Язык: Английский

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Selective Catalytic Synthesis of α-Alkylated Ketones and β-Disubstituted Ketones via Acceptorless Dehydrogenative Cross-Coupling of Alcohols

Organic Letters, Год журнала: 2021, Номер 23(3), С. 869 - 875

Опубликована: Янв. 21, 2021

Herein, a phosphine-free pincer ruthenium(III) catalyzed β-alkylation of secondary alcohols with primary to α-alkylated ketones and two different β-branched are reported. Notably, this transformation is environmentally benign atom efficient H2O H2 gas as the only byproducts. The protocol extended gram-scale reaction for functionalization complex vitamin E cholesterol derivatives.

Язык: Английский

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N-Methylation of Amines with Methanol in the Presence of Carbonate Salt Catalyzed by a Metal–Ligand Bifunctional Ruthenium Catalyst [(p-cymene)Ru(2,2′-bpyO)(H₂O)]

The Journal of Organic Chemistry, Год журнала: 2021, Номер 86(3), С. 2621 - 2631

Опубликована: Янв. 27, 2021

A ruthenium complex [(p-cymene)Ru(2,2′-bpyO)(H2O)] was found to be a general and efficient catalyst for the N-methylation of amines with methanol in presence carbonate salt. Moreover, series sensitive substituents, such as nitro, ester, cyano, vinyl groups, were tolerated under present conditions. It confirmed that OH units ligand are crucial catalytic activity. Notably, this research exhibited potential metal–ligand bifunctional catalysts hydrogen autotransfer process.

Язык: Английский

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Guerbet-type β-alkylation of secondary alcohols catalyzed by chromium chloride and its corresponding NNN pincer complex

Catalysis Science & Technology, Год журнала: 2022, Номер 12(15), С. 4753 - 4762

Опубликована: Янв. 1, 2022

β-Alkylation of alcohols has been efficiently accomplished using readily available 3d metal Cr under microwave conditions in air. Well-defined molecular is involved with a KIE 7.33 and insertion α-alkylated ketone into Cr–H bond as the RDS.

Язык: Английский

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A Proton‐Responsive Pyridyl(benzamide)‐Functionalized NHC Ligand on Ir Complex for Alkylation of Ketones and Secondary Alcohols

Chemistry - A European Journal, Год журнала: 2021, Номер 27(41), С. 10737 - 10748

Опубликована: Май 17, 2021

Abstract A Cp*Ir(III) complex ( 1 ) of a newly designed ligand L featuring proton‐responsive pyridyl(benzamide) appended on N ‐ heterocyclic carbene (NHC) has been synthesized. The molecular structure reveals dearomatized form the ligand. protonation with HBF 4 in tetrahydrofuran gives corresponding aromatized [Cp*Ir(L H)Cl]BF 2 ). Both compounds are characterized spectroscopically and by X‐ray crystallography. acid is examined H NMR UV‐vis spectra. character exploited for catalyzing α ‐alkylation ketones β secondary alcohols using primary as alkylating agents through hydrogen‐borrowing methodology. Compound an effective catalyst these reactions exhibits superior activity comparison to structurally similar iridium )Cl]PF 6 3 lacking pendant amide moiety. catalytic alkylation wide substrate scope, low base loadings, short reaction time. efficacy also demonstrated syntheses quinoline lactone derivatives via acceptorless dehydrogenation, selective two steroids, pregnenolone testosterone. Detailed mechanistic investigations DFT calculations substantiate role process.

Язык: Английский

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Catalytic Formal Conjugate Addition: Direct Synthesis of δ-Hydroxynitriles from Nitriles and Allylic Alcohols

ACS Catalysis, Год журнала: 2022, Номер 12(4), С. 2191 - 2204

Опубликована: Янв. 28, 2022

Alcohols and nitrile functionalities have widespread applications in biochemical chemical synthesis. Catalytic transformations involving C–C bond formation relying on unsaturated coupling partners create important pathways for processes synthetic, material, medicinal chemistry. The discovery of a simple selective nitriles with allylic alcohols catalyzed by ruthenium pincer complex is described, which tolerates reactive functional groups such as carbamate, sulfonate, olefin, cyano, trifluoromethyl-substituted benzyl nitriles. Homo also provided 1,4-addition products following the isomerization double bonds. Mechanistic studies supported that initially undergo oxidation catalyst to α,β-unsaturated carbonyl compounds followed 1,4-conjugate addition base subsequent catalytic reduction functionality, leading δ-hydroxynitrile products. cycle this tandem process established density theory studies. Remarkably, anipamil drug successfully synthesized using protocol. utility synthesis biologically active molecules their further functionalization are demonstrated.

Язык: Английский

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Pincer-Cobalt-Catalyzed Guerbet-Type β-Alkylation of Alcohols in Air under Microwave Conditions

Organometallics, Год журнала: 2022, Номер 41(22), С. 3387 - 3398

Опубликована: Авг. 5, 2022

Pincer complexes of the type (R2NNN)CoCl2 (R = iPr, tBu, Cy, Ph, p-F-C6H4) derived from environmentally benign, earth-abundant, and inexpensive base metal cobalt have been synthesized that exist in equilibrium with [(R2NNN)2Co]CoCl4. Among these complexes, (iPr2NNN)CoCl2 has found to be highly efficient for catalytic β-alkylation alcohols air at 140 °C. While pincer-Co (0.0025 mol %)-catalyzed presence NaOtBu (2.5 %) took 24 h (85%, 34000 TON 1417 TO/h) under conventional heating (140 °C), corresponding reaction microwave conditions °C 75 W) was complete only 2 comparable yields (83%, 33200 TON), albeit a better TOF (16600 TO/h). In contrast, CoCl2 otherwise identical leads lower both (66%, 26400 1100 (61%, 24400 12200 The system successfully implemented (39 examples) accomplish secondary several primary alcohols. Well-defined molecular Co(II) species are involved during catalysis, as inferred HRMS hot-filtration experiments. EPR studies magnetic moment measurements using Evans method demonstrate Co remains its +2 state an octahedral geometry throughout reaction. Pivotal evidence involvement β-hydride elimination leading acetophenone RDS catalyzed is obtained competitive deuterium labeling experiments, which indicative KIE 6.14. current report on base-metal catalysis high unprecedented turnovers (33200 16600 very short time (2 h) offers exciting atom-economical greener possibilities class synthetically valuable Guerbet-type reactions.

Язык: Английский

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NNN Pincer-Manganese-Catalyzed Guerbet-Type β-Alkylation of Alcohols under Microwave Irradiation

Organometallics, Год журнала: 2023, Номер 42(14), С. 1818 - 1831

Опубликована: Июнь 24, 2023

A series of manganese carbonyl complexes based on bis(imino)pyridine ligands the type R2NNN (R = Cy, iPr, Ph, p-FC6H4) were synthesized. While complex appears to be an NN bidentate-Mn(I) triscarbonyl species in solid state, solution, there is a gradual loss carbon monoxide leading first NNN pincer-Mn(I) biscarbonyl complex, which finally disproportionates pincer-Mn(II) dibromide and pincer-Mn(0) complex. Evidence for this transformation has been obtained from single-crystal X-ray diffraction, IR, EPR, HRMS analysis. The apparently faster with cyclohexyl-substituted than others. considered (0.05 mol %) utilized catalyzing β-alkylation secondary alcohols at 140 °C air under conventional heating (12 h), as well microwave (2 h) presence 2.5 % NaOtBu. Among complexes, catalyst (p-FC6H4NNN)Mn(CO)2Br was found highly efficient. heating, maximum 92% (1840 TON 153 TOs/h) β-alkylated product obtained; provided 85% yield (1700 850 just 2 h. catalytic system successfully implemented alkylate several other alcohols, (35 examples). analyses indicate intermediates cycle both pincer-Mn(II)/Mn(0) couple. Deuterium labeling studies point involvement C–H bond activation rate-determining step (RDS) kinetic isotope effect (KIE) 9.0.

Язык: Английский

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Recent Advances in π-Stacking Interaction-Controlled Asymmetric Synthesis

Molecules, Год журнала: 2024, Номер 29(7), С. 1454 - 1454

Опубликована: Март 24, 2024

The π-stacking interaction is one of the most important intramolecular and intermolecular noncovalent interactions in organic chemistry. It plays an role stabilizing some structures transition states certain reactions via both interactions, facilitating different selectivities, such as chemo-, regio-, stereoselectivities. This minireview focuses on recent examples interaction-controlled asymmetric synthesis, including auxiliary-induced kinetic resolution, synthesis helicenes heterohelicenes, multilayer 3D chiral molecules.

Язык: Английский

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From selective transfer hydrogenation to selective hydrogen auto-transfer process: An efficient method for the synthesis of alkenyl ketones via iridium-catalyzed α-alkylation of ketones with alkenyl alcohols

Journal of Catalysis, Год журнала: 2021, Номер 402, С. 335 - 343

Опубликована: Авг. 26, 2021

Язык: Английский

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