Synthesis and luminescent properties of zinc(II) complexes with iodo- and bromosubstituted 2,2′-dipyrrines

This article compares spectroscopic properties of the series of dipyrromethene dyes, namely their complexes of boron (III), zinc(II) and cadmium(II) with the halogenated ligands of the same structure. Absorption and emission spectra, lifetimes of long-lived emission and quantum yields of luminescence were studied as the functions of molecular structure of dipyrromethene complexes. The role of the position and nature of a substituent in a ligand, polarity of a solvent and temperature of media were also investigated. The studies demonstrate that replacing the central atom boron(III) by zinc(II) decreases the fluorescence quantum yield, indicating the increased role of non-radiative processes in excitation energy deactivations such as intersystem crossings. In addition, according to the heavy atom effect, the efficiency of intersystem crossings in halogen-substituted zinc(II) and cadmium(II) dipyrromethene complexes is higher than in the corresponding boron fluoride dipyrromethenes (BODIPY), which leads to increase in phosphorescence at low temperatures (frozen solutions). The obtained results make it possible to carry out further investigations of potential sensory properties that are required for systematic use of halogenated dipyrromethene complexes for the creation of modern optical oxygen sensors and singlet oxygen photosensitizers for photodynamic therapy or photocatalytic oxidative reactions.

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Section: Methodsmentioning

confidence: 99%

“…Analytical chemistry of the studied compounds has been performed by means of mass, IR and NMR spectroscopy at the G.A. Krestov Institute of Solution Chemistry at the Russian Academy of Sciences [22,23]. Analytically pure ethanol, propanol-2, chloroform and cyclohexane were used as solvents (all HPLC grade).…”

Section: Methodsmentioning

confidence: 99%

Photonics of Halogenated Zinc(II) and Cadmium(II) Dipyrromethene Complexes

2022

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“…Krestov Institute of Solution Chemistry of the Russian Academy of Sciences (Ivanovo). The descriptions of the synthesis and control of the purity of the structure using thin-layer chromatography and IR spectroscopy are described in [31][32][33]. Structural formulas of 3,3 ,5,5 -tetramethyl-4,4dibromo-2,2 -dipyrromethene complexes coordinated with BF 2 , Zn, and Cd, which are abbreviated in this work as Br 2 (CH 3 ) 4 BODIPY, Zn[Br 2 (CH 3 ) 4 dpm] 2 , and Cd[Br 2 (CH 3 ) 4 dpm] 2 , respectively, are shown in Figure 5.…”

Section: Methodsmentioning

confidence: 99%

Stability of Dibromo-Dipyrromethene Complexes Coordinated with B, Zn, and Cd in Solutions of Various Acidities

Aksenova

Pomogaev

2022

Molecules

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The spectral luminescent properties of dipyrromethenates halogenated with bromine on both ends of the long axis and coordinated using boron fluoride, zinc, or cadmium in neutral ethanol and acidified with hydrochloric acid solutions were studied. The constants of the acid–base equilibrium of the complexes in the proton-donor solvents in the ground and excited states was determined. The mechanisms of complex protonation were discussed, depending on the structure of the compounds. The electronic structures of the neutral and protonated compounds were modeled and analyzed based on the quantum-chemical method. The structures and spectral-luminescence properties were calculated using the SMD model of ethanol solvent using the TD-DFT theory with the B3LYP functional and the composite def2-SVP/def2-TZVP/def2-TZVPP_ECP basis sets, depending on the atomic number of the elements.

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Synthesis and Photochemical Properties of 2,3;5,6-bis(cyclohexano)-BODIPY

et al. 2017

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The boron-dipyrromethene (BODIPY) dye containing an annelated cyclohexyl rings at the 2,3 and 5,6-positions of pyrroles has been synthesized and characterized. Photochemical properties of the obtained compound have been investigated in different individual solvents. 2,3;5,6-Bis(cyclohexano)-BODIPY exhibits intense chromophore properties with maximum of S → S band in the 543-549 nm (A from 66000 to 96000 L/mol·cm). The complex is a fluorophore with a quantum yield up to ~ 100%. The influence of solvent polarity on the spectral properties was evaluated. To better understand the spectroscopic results, quantum chemical calculations were carried out. Photostability of dye was studied.Graphical Abstract.

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Synthesis and luminescent properties of zinc(II) complexes with iodo- and bromosubstituted 2,2′-dipyrrines

Cited by 13 publications

References 21 publications

Photonics of Halogenated Zinc(II) and Cadmium(II) Dipyrromethene Complexes

Photonics of Halogenated Zinc(II) and Cadmium(II) Dipyrromethene Complexes

Stability of Dibromo-Dipyrromethene Complexes Coordinated with B, Zn, and Cd in Solutions of Various Acidities

Synthesis and Photochemical Properties of 2,3;5,6-bis(cyclohexano)-BODIPY

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