Correction: A theoretical study on the on-off phosphorescence of novel Pt(ii)/Pt(iv)-bisphenylpyridinylmethane complexes.

[This corrects the article DOI: 10.1039/D2RA03060H.].

Correction: A combined crystallography and DFT study on ring-shaped cucurbit[n]urils: structures, surface character, and host-guest recognition.

[This corrects the article DOI: 10.1039/D2RA00797E.].

Study of the electronic effect and quantitative spectra predictions of o-methoxyaniline-terminated monoazonaphthols: a combined experimental and DFT study.

A combined experimental and density functional theory (DFT) study on the UV-Vis spectra of o-methoxyaniline-terminated mono azo dyes was conducted. By applying time-dependent-DFT calculations, details of excitation processes were determined and visualization by hole-electron analysis was undertaken. Fragment-divided analysis revealed the contributions of different parts of the structures for the UV-Vis spectra, that richer/poorer electron density on aromatic rings lead to greater/less maximum absorption wavelengths (λmax) and larger/smaller half peak width (W1/2). Combining theoretical prediction with experimental verification, we answered the question of how the electronegativities of substituents affected the electron densities and how it affected the spectra. In addition, a linear model connecting the λmax and W1/2 to the chemical shifts obtained by NMR spectroscopy was constructed, which laid the foundation for construction of a spectral library.

A theoretical study on the on-off phosphorescence of novel Pt(ii)/Pt(iv)-bisphenylpyridinylmethane complexes.

An in-depth theoretical study on the Pt(ii)/Pt(iv)-bisphenylpyridinylmethane complexes was carried out, which focused on the geometric/electronic structures, excitation procedures, on-off phosphorescence mechanisms, and structure-optical performance relationships. The key roles of the linkages (LK) connected in the middle of phenylpyridines were carefully investigated using multiple wavefunction analysis methods, such as non-covalent interaction (NCI) visualizations and natural bond orbital (NBO) studies. The phosphorescence-off phenomenon was considered by hole-electron analysis and visualizations, spin-orbit coupling (SOC) studies, and NBO analysis. Through these investigations, the relationship of the substituents in LK and the optical performances were revealed, as well as the fundamental principles of the phosphorescence-quenching mechanism in Pt(iv) complexes, which pave the way for further performance/structural renovation works. In addition, an intuitive visualization method was developed using a heatmap to quantitatively express the SOC matrix elementary (SOCME), which is helpful for big data simplification for phosphorescence analysis.

A combined crystallography and DFT study on ring-shaped Cucurbit[n]urils: structures, surface character, and host-guest recognition.

A combined crystallography and DFT study of cucurbit[n]urils (n = 5-8, 10) was carried out, and PBE0 was certified to be the most rational density functional method for optimization task. Steric hindrance and electronic effect of the hindered lone pair electrons in cucurbit[n]urils were qualitatively measured by bond order analysis, lone pair electron (LP) visualization and electrostatic potential (ESP) study. Together with energy decomposition analysis of some selected host-guest systems, we quantitatively verified the effect of size/cavity and noncovalent interaction in host-guest recognition. This solid study revealed that lone pairs electrons affect not only on host-guest identification mode but also on geometry stability, which pave the avenue for further sophisticated applications.

Copper-Catalyzed Enantioselective C-H Arylation between 2-Arylindoles and Hypervalent Iodine Reagents.

The copper-catalyzed enantioselective C-H arylation between 2-arylindoles and hypervalent iodine reagents has been successfully developed, which provides a convenient and economical route to the highly atroposelective synthesis of axially chiral indole derivatives with a 2-aryl structure (up to 99% ee). Density functional theory calculations and wave function analysis show that the key "sandwich" intermediate leads to high enantioselectivity of the reaction.

Novel recognition mechanism based on oxidative addition of Pt(II) complex-based luminescent probes for hypochlorite ion detection.

Platinum(II) complexes are the most commonly used anticancer drugs and potential optical materials, but the detectability of Pt(II) complex-based probes is seldom reported. In our previous work, a tetradentate Pt(II) complex Pt-CHO was utilised as a 'turn-off' probe to detect ClO- and image cancer cells. However, the recognition mechanism has not been completely clarified and there are still doubts. In this work, three Pt(II) complexes, Pt-H, Pt-CHO and Pt-COOH, were developed to elucidate the mechanism of this class of complexes and refine their property studies. As a result, the UV-visible absorption and luminescence emission experiments, as well as the mass spectrum, proved that the oxidation of Pt(II) to Pt(IV) was the real reason for luminescence quenching, which has nothing to do with aldehyde groups. This first reported mechanism introduces a new type of ClO- probe based on Pt(II) complexes, thereby expanding the application fields of platinum complexes. Moreover, the quantum yield measurements, the effect of biomolecules and reversibility were studied to improve the properties of the probes. Theoretical calculations were used to gain an in-depth understanding of optical characteristics and related mechanisms. The cell imaging of RAW264.7 cells under endogenous ClO- proved the potential of the probes in bioimaging.

Ru(II)-Catalyzed and acidity-controlled tunable [5+1]/[5+2] annulation for building ring-fused quinazolines and 1,3-benzodiazepines.

The Ru(ii)-catalyzed tunable [5+1]/[5+2] annulation of N-benzo[d]imidazole indolines with propargyl carbonates has been realized for the divergent synthesis of ring-fused quinazolines and 1,3-benzodiazepines bearing various functional groups. These transformations represent an efficient and practical strategy in constructing complex heterocycles via diversified C-H functionalization. A distinctive acidity-controlled reaction manner has been clarified to account for the chemoselectivity.

Synergistic Dual Directing Groups-Enabled Diastereoselective C-H Cyclopropylation via Rh(III)-Catalyzed Couplings with Cyclopropenyl Alcohols.

By using a synergistic dual directing group-assisted C-H activation strategy and simply modifying the reaction conditions, we realized a robust and general Cp*Rh(III)-catalyzed C-H cyclopropylation of N-acetoxybenzamides with cyclopropenyl alcohols, providing regio-, chemo-, and diastereoselective access to ortho trans- and cis-1,1-dimethylcyclopropane-functionalized benzamides in a redox-neutral and controllable manner. Experimental and density functional theory studies clarify the roles of the NH-OAc and OH groups and deduce two distinct Rh(III)-Rh(V)-Rh(III) pathways for presenting such selectivity.

Highly ordered macroporous dual-element-doped carbon from metal-organic frameworks for catalyzing oxygen reduction.

Multiple heteroatom-doped carbons with 3D ordered macro/meso-microporous structures have not been realized by simple carbonization of metal-organic frameworks (MOFs). Herein, ordered macroporous phosphorus- and nitrogen-doped carbon (M-PNC) is prepared successfully by carbonization of double-solvent-induced MOF/polystyrene sphere (PS) precursors accompanied with spontaneous removal of the PS template, followed by post-doping. M-PNC shows a high specific surface area of 837 m2 g-1, nitrogen doping of 3.17 at%, and phosphorus doping of 1.12 at%. Thanks to the hierarchical structure, high specific surface area, and multiple heteroatom-doping, M-PNC exhibits unusual catalytic activity as an electrocatalyst for the oxygen reduction reaction. Computational calculation reveals that the P[double bond, length as m-dash]O group helps stabilize the adsorption of intermediates, and the position of P[double bond, length as m-dash]O relative to graphitic N significantly improves the activity of the adjacent carbons for electrocatalysis.

Rhodium(III)-Catalyzed Enantio- and Diastereoselective C-H Cyclopropylation of N-Phenoxylsulfonamides: Combined Experimental and Computational Studies.

Cyclopropane rings are a prominent structural motif in biologically active molecules. Enantio- and diastereoselective construction of cyclopropanes through C-H activation of arenes and coupling with readily available cyclopropenes is highly appealing but remains a challenge. A dual directing-group-assisted C-H activation strategy was used to realize mild and redox-neutral RhIII -catalyzed C-H activation and cyclopropylation of N-phenoxylsulfonamides in a highly enantioselective, diastereoselective, and regioselective fashion with cyclopropenyl secondary alcohols as a cyclopropylating reagent. Synthetic applications are demonstrated to highlight the potential of the developed method. Integrated experimental and computational mechanistic studies revealed that the reaction proceeds via a RhV nitrenoid intermediate, and Noyori-type outer sphere concerted proton-hydride transfer from the secondary alcohol to the Rh=N bond produces the observed trans selectivity.

Stereoselective ß-F Elimination Enabled Redox-Neutral [4 + 1] Annulation via Rh(III)-Catalyzed C-H Activation: Access to Z-Monofluoroalkenyl Dihydrobenzo[ d]isoxazole Framework.

An efficient and practical Rh(III)-catalyzed redox-neutral [4 + 1] annulation of N-phenoxy amides with α, α-difluoromethylene alkynes has been realized to give direct access to the Z-configured monofluoroalkenyl dihydrobenzo[ d]isoxazole framework with broad substrate compatibility and good functional group tolerance, which was further enhanced by the late-stage C-H modification of complex bioactive compounds. Subsequent density functional theory calculations revealed that the stereoselective ß-F elimination involving an allene species played a decisive role in determining the reaction outcome and such Z-selectivity.

Chemodivergent Couplings of N-Arylureas and Methyleneoxetanones via Rh(III)-Catalyzed and Solvent-Controlled C-H Activation.

The efficient couplings of diverse N-arylureas and methyleneoxetanones have been realized via Rh(III)-catalyzed and solvent-controlled chemoselective C-H functionalization, which involved the tunable ß-H elimination and ß-O elimination processes, thereby giving divergent access to quinolin-2(1 H)-ones and ortho-allylated N-arylureas with broad substrate compatibility and good functional group tolerance. the divergent synthetic utilities of the transformations have also been exemplified by subsequently tandem C-H allylation, unsymmetrical C-H functionalization, alternative reaction mode, as well as removal of the carbamoyl group.

Bran-New Four-Molecule and Five-Molecule Cascade Reactions for One-Pot Synthesis of Pyrano[3,2-c]chromen-5-ones and Spiro[benzo[b][1,4]diazepine-2,2'-pyrano[3,2-c]chromen]-5'-ones under Catalyst- and Solvent-Free Conditions.

Herein, two versatile bran-new methods have been developed for building three new kinds of complicated-framework compounds including 2,4,4-trimethyl-2-(phenylamino)-3,4-dihydro-2H,5H-pyrano[3,2-c]chromen-5-ones, 4,4,4',4'-tetramethyl-1,3,3',4,4',5-hexahydro-5'H-spiro-[benzo[b][1,4]diazepine-2,2'-pyrano[3,2-c]-chromen]-5'-ones, and 2,2,4',4'-tetramethyl-2,3,3',4'-tetrahydro-5H,5'H-spiro[benzo[b][1,4]-oxazepine-4,2'-pyrano[3,2-c]chromen]-5'-ones in a one-pot manner via four-molecule and five-molecule cascade reactions of commercially available 4-hydroxychromen-2-one, substituted anilines, and acetone. In consideration of these impressive features including no need of additional catalysts and solvents, moderate to good yields, excellent site-selectivity, and broad substrate/functional group tolerance, we believe that the two present protocols should have the potential for broad synthetic utility.

Study on the design, synthesis and structure-activity relationships of new thiosemicarbazone compounds as tyrosinase inhibitors.

52 Structure-based thiosemicarbazone compounds bearing various substituted-lipophilic part, including substituted-benzaldehyde, substituted-phenylalkan-1-one and their biphenyl-type thiosemicarbazone analogs, were designed, synthesized and evaluated as new tyrosinase inhibitors. The results demonstrated that 22 compounds have potent inhibitory activities against tyrosinase with the IC50 value of lower than 1.0 µM. On the basis of the obtained experimental data, the structure-activity relationships (SARs) were rationally derived. Besides, the inhibition mechanism and the inhibitory kinetics of selected compounds 3d and 6e were investigated, revealing that such type of compounds were belonged to the reversible and competitive tyrosinase inhibitors. To verify the safety of these developed thiosemicarbazone compounds, four randomly selected compounds 3d, 4e, 6a and 9a were also tested in 293T cell line for the evaluation of the cytotoxicity. Interestingly, all these compounds almost did not perform any toxicity to 293T cells even at a high concentration of 1000 µmol/L. Taken together, these results suggested that such compounds could serve as the highly efficient and more safe candidates for the treatment of tyrosinase-related disorders.

Rational design, synthesis and structure-activity relationships of 4-alkoxy- and 4-acyloxy-phenylethylenethiosemicarbazone analogues as novel tyrosinase inhibitors.

In continuing our program aimed to search for potent compounds as highly efficient tyrosinase inhibitors, here a series of novel 4-alkoxy- and 4-acyloxy-phenylethylenethiosemicarbazone analogues were designed, synthesized and their biological activities on mushroom tyrosinase were evaluated. Notably, most of compounds displayed remarkable tyrosinase inhibitory activities with IC50 value of lower than 1.0µM. Furthermore, the structure-activity relationships (SARs) were discussed and the inhibition mechanism and the inhibitory kinetics of selected compounds 7k and 8d were also investigated. Taken together, these results suggested that such compounds could serve as the promising candidates for the treatment of tyrosinase-related disorders and further development of such compounds might be of great interest.

Structure-based modification of 3-/4-aminoacetophenones giving a profound change of activity on tyrosinase: from potent activators to highly efficient inhibitors.

In this study, we developed 3-/4-aminoacetophenones and their structure-based 3-/4-aminophenylethylidenethiosemicarbazide derivatives, respectively, as novel tyrosinase activators and inhibitors. Notably, all the obtained thiosemicarbazones displayed more potent tyrosinase inhibitory activities than kojic acid. Especially, compound 7k was found to be the most active tyrosinase inhibitor with IC50 value of 0.291 µM. The structure-activity relationships (SARs) analysis showed that: (1) the amine group was absolutely necessarily for determining the tyrosinase activation activity; (2) the introduction of thiosemicarbazide group played a very vital role in transforming tyrosinase activators into tyrosinase inhibitors; (3) the phenylethylenethiosemicarbazide moiety was crucial for determining the tyrosinase inhibitory activity; (4) the type of acyl group had no obvious effect on the inhibitory activity; (5) the position of amide substituent on the phenyl ring influenced the tyrosinase inhibitory potency. Moreover, the inhibition mechanism and inhibition kinetics study revealed that compound 7k was reversible and non-competitive inhibitor, and compound 8h was reversible and competitive-uncompetitive mixed-II type inhibitor.