Synthesis, Structures, Photoluminescent Behaviors, and DFT Studies of Novel Aluminum Complexes Containing Phenoxybenzotriazole Derivatives

Abstract

Treatment of AlMe) and subsequent addition of ROH afford monomeric and heteroleptic (OR)AlL 2 complexes [R =

Cytotoxicity studies, DNA interaction and protein binding of new Al (III), Ga (III) and In (III) complexes with 5‐hydroxyflavone

“…The coordination spheres around the metal center in complexes (1) (Figure ), (2) (Figure S4 and S5), (3) (Figure S6) involve the following atoms: O2, O3, O4, O5, O6, O7 (belonging to the deprotonated 5‐hydroxyflavone). Bond lengths for M‐O are comparable with previously reported results of Al, Ga, In complexes …”

Adding a Structural Context to the Deprotometalation and Trans‐Metal Trapping Chemistry of Phenyl‐Substituted Benzotriazole

“…[9] An added incentive for including aluminium is the paucityo fc rystallographically characteriseda luminium benzotriazoles with ar are exception being as eries of phenoxybenzotriazole derivatives studied for their photoluminescent properties. [10] In the lithium-aluminiums ystem in question, LiTMP (TMP = 2,2,6,6-tetramethylpiperidide) performst he metalation of the CÀHs ubstrate, whereas the dialkylaluminium amide iBu 2 Al(TMP) performs the trans-metal trapping of the developing C À carbanion. As was explained elsewhere, [8] we do not use the more commont erm transmetalation as it usually signifies the exchange of metals in separate compounds, whereas herein, the aluminium compound inserts into the CÀLi bond to trap and simultaneously stabiliset he carbanion within the one mixed lithium-aluminiumc ompound, hence,t rans-metal trapping seems more appropriate.…”

“…To the best of our knowledge, there are no previous examples of CÀHa luminated benzotriazolyl-basedc rystal structures for direct comparison with 3 and 4.B enzotriazole derivatives substituted by phenol appendages at the 2HÀNp osition have been structurally determined, but these do not contain AlÀC bonds, because their Al centresi nteract only with Na nd O atoms. [10] Allt he AlÀCb onds within 3 and 4 fall in the narrow range 2.003(3) [16] …”

A Direct Stereoselective Preparation of a Fish Pheromone and Application of the Zinc Porphyrin Tweezer Chiroptical Protocol in Its Stereochemical Assignment

“…Molecular modeling Density Functional Theory (DFT) calculations at the (R)B3LYP/6‐31G(d) level were computed to elucidate the pathway of the reduction of the carbonyl at C20 to yield either the pheromone, (20R)-1 , or its epimer (20S)-1 . The ground state equilibrium geometries, i.e., lowest energy conformers, of all synthesized molecules and suggested stable intermediates ( [2‐HAlO] , [6] ‐ and [6‐BH 3 ] ) were optimized in the gas phase at 298 K. All ground states were true minima with no imaginary vibrational frequencies (see Electronic Supporting Information for energy differences between conformers of the optimized structures) …”

“…The ground state equilibrium geometries, i.e., lowest energy conformers, of all synthesized molecules and suggested stable intermediates ([2-HAlO], [6]and [6-BH 3 ]) were optimized in the gas phase at 298 K. All ground states were true minima with no imaginary vibrational frequencies (see Electronic Supporting Information for energy differences between conformers of the optimized structures). [31][32][33][34][35] The equilibrium geometry of methylketone 6 has an H-bond between the OH at C17 and the oxygen of the carbonyl at C20. This exposes the re face of the carbonyl toward nucleophilic attack, as the opposite si face is hindered by the C18-methyl group (Fig.…”