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Carbazole-based aggregation-induced phosphorescent emission-active gold(I) complexes with various phosphorescent mechanochromisms.

ABSTRACT: A series of carbazole-containing gold(I) complexes modified with different substituents were successfully designed and synthesized, and their molecular structures were characterized by nuclear magnetic resonance spectroscopy and mass spectrometry. The aggregation-induced behaviors of these gold(I) complexes were studied by ultraviolet/visible and photoluminescence spectroscopy. Meanwhile, their mechanical force-responsive emissive properties were also investigated via solid-state photoluminescence spectroscopy. Interestingly, all these gold(I)-based luminogenic molecules were capable of exhibiting aggregation-induced phosphorescent emission phenomena. Furthermore, their solids of three gold(I) complexes displayed contrasting mechano-responsive phosphorescence features. More specifically, trifluoromethyl or methoxyl-substituted luminophores 1 and 3 demonstrated mechanochromic behaviors involving blue-shifted phosphorescence changes, and their mechanoluminochromic phenomena were reversible. However, the solid-state phosphorescence of phenyl-substituted luminophor 2 was not sensitive to external mechanical force.

SUBMITTER: Chen Z

PROVIDER: S-EPMC9752811 | biostudies-literature | 2022

REPOSITORIES: biostudies-literature

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Carbazole-based aggregation-induced phosphorescent emission-active gold(I) complexes with various phosphorescent mechanochromisms.

Chen Zhao Z Deng Xiao-Wen XW Wang Xiao-Yan XY Wang An-Qi AQ Luo Wen-Tao WT

Frontiers in chemistry 20221201

A series of carbazole-containing gold(I) complexes modified with different substituents were successfully designed and synthesized, and their molecular structures were characterized by nuclear magnetic resonance spectroscopy and mass spectrometry. The aggregation-induced behaviors of these gold(I) complexes were studied by ultraviolet/visible and photoluminescence spectroscopy. Meanwhile, their mechanical force-responsive emissive properties were also investigated <i>via</i> solid-state photolum ...[more]

PMID: 36531308

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Project description:Positional isomers of zinc-nitrobenzoate complexes possessing pyridine -3-(or-4-) carboxamide are used for a comparative theoretical and experimental study to understand their utility as model complexes to understand the role of metal-to-ligand charge transfer in aggregation-induced emission (AIE). Among the five different model zinc complexes, four of them are non-ionic, and one is an ionic complex. The frontier molecular energy levels of different combinations of the positional isomeric complexes and the absorption maximum were ascertained by density functional theory calculations. The PolyQ value obtained from solid samples of each complex is different. Shifts in the emissions to higher wavelengths than the expected emission for the S1 to S0 transition were observed due to aggregations. The highest value of PolyQ among the complexes was 13.56% observed for emission at 439 nm (λex = 350) of the non-ionic complex, namely, (di-aqua)bis(pyridine-3-carboxamide)di(2-nitrobenzoato)zinc(II) monohydrate. Close resemblance in emission lifetime decay profiles of the solid samples of those complexes and the respective solutions of those complexes in dimethyl sulfoxide with or without water showed a common trend, suggesting aggregation-induced emission in each case. Aggregation-induced emission caused by adding water in dimethyl sulfoxide solution of each complex showed an initial increase without a shift in the emission wavelength followed by a quenching with a shift of the respective emission peak to a short wavelength. Dynamic light scattering studies showed an increase in the average particle sizes upon an increase in the concentration of water. This indicated initial participation of water molecules to form aggregates with the complexes, favoring an increase in the AIE intensity. Aggregation of each complex changes with the concentration of water, and an increase in the concentration of water beyond a characteristic limit causes lowering of the emission intensity to the short wavelength.

Dataset Information

Carbazole-based aggregation-induced phosphorescent emission-active gold(I) complexes with various phosphorescent mechanochromisms.

Publications

Carbazole-based aggregation-induced phosphorescent emission-active gold(I) complexes with various phosphorescent mechanochromisms.

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