A blue light emitting pyrene derivative, 1-methyl benzoate-pyrene (MB-Py), was synthesized by employing a pyrene moiety as the parent linked with a small electron-donating group, methyl benzoate. Owing to the introduction of methyl benzoate, there is an evident twisted configuration between the methyl benzoate moiety and the central pyrene core with a dihedral angle of 56°, confirmed by density functional theory (DFT) calculations. The basic photophysical, electrochemical and electrogenerated chemiluminescence (ECL) properties of MB-Py together with those of the parent pyrene (Py) and the analogue benzo[α]pyrene (Bz-Py) in MeCN : Bz (v/v = 1 : 1) were extensively characterized for the first time. The electrochemical behavior of MB-Py showed a quasi-reversible one-electron oxidation (E1/2 = +1.11 V vs. SCE) and two reversible closely spaced consecutive one-electron reductions (E1/2,1 = −2.12 V and E1/2,2 = −2.27 V vs. SCE). This redox behavior was confirmed by CV digital simulations and was consistent with the frontier molecular orbitals calculated. It was found that, unlike its parent Py and analogue Bz-Py, MB-Py showed a single-peaked absorption (343 nm) and a blue monomer photoluminescence (PL) emission (428 nm) with a large Stokes shift (85 nm). The electrogenerated radical ions of MB-Py are stable enough to produce an efficient ECL emission (439 nm) through ion annihilation with the S-route. The ECL spectra of MB-Py obtained in both the ion annihilation and coreactant processes are similar to the monomer PL spectrum. This nonplanar twisted conformation pyrene derivative imparts steric hindrance, prevents excimer formation and results in a high PL efficiency and efficient, stable blue ECL monomer emission. Owing to their rigid planar structures, Py and Bz-Py exhibited monomer and excimer blue-violet PL emissions and cyan/green ECL emissions, and could not be used as appropriate blue luminophores.

An efficient synthesis of α-acylphosphoranes by palladium-catalyzed carbonylation of aryl iodides with carbon monoxide and stabilized phosphonium ylides has been developed. Featuring 44 examples, the protocol displayed a wide substrate scope under mild reaction conditions, showcasing its potential in synthetic organic chemistry.

By the use of 1-chloro-1,2-benziodoxol-3-one, an age-old reagent, the practical and efficient chlorination method is achieved. This hypervalent iodine reagent is amenable not only to the chlorination of nitrogen-containing heterocycles but also to selected classes of arenes, BODIPY dyes, and pharmaceuticals. In addition, the advantages, such as easy preparation and recyclable, air- and moisture-stable, in combination with the success in a gram-scale experiment grant this reagent great potential for industrial application.

A novel and efficient protocol for the synthesis of amides is reported which employs a BODIPY catalyzed oxidative amidation reaction between aromatic aldehydes and amines under visible light. Compared with the known Ru or Ir molecular catalysts and other organic dyes, the BODIPY catalyst showed higher reactivity toward this reaction. Mechanistic studies reveal that dioxygen could be activated through an ET and a SET pathway, forming active peroxides in situ, which are vital for the key step of the reaction, i.e. the oxidation of hemiaminal to amide. The broad substrate scope and mild reaction conditions make this reaction practically useful and environmentally friendly for the synthesis of amide compounds.

The first allylic carbonylation reaction of allylic acetates with aryl boronic acids under carbon monoxide has been developed. Using Pd–PCy3 as a catalyst, a wide spectrum of allylic acetates was carbonylated in the presence of various aryl boronic acids, affording α,β-unsaturated aryl ketones in good to excellent yields. Preliminary studies indicate that carbon monoxide always inserts at the least substituted terminal allylic carbon and the resulting β,γ-unsaturated aryl ketones generally isomerise to the ketones obtained.

An unprecedented Rh-catalyzed direct methylation of ketones with N,N-dimethylformamide (DMF) is disclosed. The reaction shows a broad substrate scope, tolerating both aryl and alkyl ketones with various substituents. Mechanistic studies suggest that DMF delivers a methylene fragment followed by a hydride in the methylation process.

The first examples of a Pd-catalyzed carbonylation of aryl boronic acids with sp3 carbon partners are presented. Various boronic acids were shown to react with 1,3-diesters and 1,3-diketones to afford structurally unique carbonyl compounds. By employing 2-substituted 1,3-diesters, synthetically-challenging quaternary carbon centres were accessed. In total, 42 examples of aryl carbonyl compounds were prepared in moderate to good yields. The catalytic system features the use of a bidentated phosphine ligand and a relatively low CO pressure (5 atm), providing an easy, alternative method for the preparation of triketones.

Cyclometalated iridium complexes are shown to be excellent catalysts for transfer hydrogenation of carbonyl compounds in water using formate as a hydrogen source. A wide range of ketones and aldehydes have been reduced at 0.05% catalyst loading with no need for any organic solvents. Solution pH is found to play a critical role, with acidic conditions needed for fast transfer hydrogenation.

An efficient method for the preparation of 3-acylindoles has been developed, which centres on the palladium-catalyzed regioselective oxidative Heck reaction of N-protected indoles with electron-rich olefins.

A convenient method has been developed, which allows for the direct transformation of aryl iodides into the corresponding carboxylic acid anhydrides viaPd-catalyzed carbonylation under atmospheric CO pressure.

A novel and efficient protocol for the synthesis of amides is reported which employs a BODIPY catalyzed oxidative amidation reaction between aromatic aldehydes and amines under visible light. Compared with the known Ru or Ir molecular catalysts and other organic dyes, the BODIPY catalyst showed higher reactivity toward this reaction. Mechanistic studies reveal that dioxygen could be activated through an ET and a SET pathway, forming active peroxides in situ, which are vital for the key step of the reaction, i.e. the oxidation of hemiaminal to amide. The broad substrate scope and mild reaction conditions make this reaction practically useful and environmentally friendly for the synthesis of amide compounds.

The first examples of a Pd-catalyzed carbonylation of aryl boronic acids with sp3 carbon partners are presented. Various boronic acids were shown to react with 1,3-diesters and 1,3-diketones to afford structurally unique carbonyl compounds. By employing 2-substituted 1,3-diesters, synthetically-challenging quaternary carbon centres were accessed. In total, 42 examples of aryl carbonyl compounds were prepared in moderate to good yields. The catalytic system features the use of a bidentated phosphine ligand and a relatively low CO pressure (5 atm), providing an easy, alternative method for the preparation of triketones.

A convenient method has been developed, which allows for the direct transformation of aryl iodides into the corresponding carboxylic acid anhydrides viaPd-catalyzed carbonylation under atmospheric CO pressure.

The first allylic carbonylation reaction of allylic acetates with aryl boronic acids under carbon monoxide has been developed. Using Pd–PCy3 as a catalyst, a wide spectrum of allylic acetates was carbonylated in the presence of various aryl boronic acids, affording α,β-unsaturated aryl ketones in good to excellent yields. Preliminary studies indicate that carbon monoxide always inserts at the least substituted terminal allylic carbon and the resulting β,γ-unsaturated aryl ketones generally isomerise to the ketones obtained.