Luminescent organic dyes containing a phenanthro[9,10-<i>D</i>]imidazole core and [Ir(N^C)(N^N)]<sup>+</sup> complexes based on the cyclometalating and diimine ligands of this type

Solomatina, Anastasia I.; Kuznetsov, K. M.; Gurzhiy, Vladislav V.; Pavlovskiy, Vladimir V.; Porsev, Vitaly V.; Ėvarestov, R. A.; Tunik, Sergey P.

doi:10.1039/d0dt00568a

Cited by 21 publications

(26 citation statements)

References 47 publications

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“…Cartesian coordinates of the optimized structure are given in a separate file (Ir0.xyz) supplied as Supporting Material , key structural characteristics are summarized in Table S1 . These data are in good agreement with the structural parameters found earlier for the closely analogous iridium complex ( Figure S38 ) [ 51 ].…”

Section: Resultssupporting

confidence: 92%

Biocompatible Ir(III) Complexes as Oxygen Sensors for Phosphorescence Lifetime Imaging

et al. 2021

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Synthesis of biocompatible near infrared phosphorescent complexes and their application in bioimaging as triplet oxygen sensors in live systems are still challenging areas of organometallic chemistry. We have designed and synthetized four novel iridium [Ir(N^C)2(N^N)]+ complexes (N^C–benzothienyl-phenanthridine based cyclometalated ligand; N^N–pyridin-phenanthroimidazol diimine chelate), decorated with oligo(ethylene glycol) groups to impart these emitters’ solubility in aqueous media, biocompatibility, and to shield them from interaction with bio-environment. These substances were fully characterized using NMR spectroscopy and ESI mass-spectrometry. The complexes exhibited excitation close to the biological “window of transparency”, NIR emission at 730 nm, and quantum yields up to 12% in water. The compounds with higher degree of the chromophore shielding possess low toxicity, bleaching stability, absence of sensitivity to variations of pH, serum, and complex concentrations. The properties of these probes as oxygen sensors for biological systems have been studied by using phosphorescence lifetime imaging experiments in different cell cultures. The results showed essential lifetime response onto variations in oxygen concentration (2.0–2.3 μs under normoxia and 2.8–3.0 μs under hypoxia conditions) in complete agreement with the calibration curves obtained “in cuvette”. The data obtained indicate that these emitters can be used as semi-quantitative oxygen sensors in biological systems.

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Section: Resultssupporting

confidence: 92%

Biocompatible Ir(III) Complexes as Oxygen Sensors for Phosphorescence Lifetime Imaging

et al. 2021

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“…Though the vast majority of C^N-cyclometalated iridium(III) chlorides are μ-chloro-bridged dimers [ 27 ], it is well documented that the increase in the steric pressure (for example, induced by phenanthroimidazole-based cyclometalated ligands) destabilizes the iridium octahedron and rare monomeric trigonal–bipyramidal chlorides can be isolated [ 28 , 29 , 30 , 31 , 32 , 33 ]. Given that the perimidine core is sterically more bulky than nitrogen-containing parts of cyclometalated ligands commonly used in iridium(III) chemistry (in most cases, pyridine ring in 2-phenylpyridines), and is rather similar to the phenanthroimidazole unit, the formation of the above monomeric species becomes possible.…”

Section: Resultsmentioning

confidence: 99%

A Panchromatic Cyclometalated Iridium Dye Based on 2-Thienyl-Perimidine

et al. 2022

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Though 2-arylperimidines have never been used in iridium(III) chemistry, the present study on structural, electronic and optical properties of N-unsubstituted and N-methylated 2-(2-thienyl)perimidines, supported by DFT/TDDFT calculations, has shown that these ligands are promising candidates for construction of light-harvesting iridium(III) complexes. In contrast to N-H perimidine, the N-methylated ligand gave the expected cyclometalated μ-chloro-bridged iridium(III) dimer which was readily converted to a cationic heteroleptic complex with 4,4′-dicarboxy-2,2′-bipyridine. The resulting iridium(III) dye exhibited panchromatic absorption up to 1000 nm and was tested in a dye-sensitized solar cell.

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“…A new ligand precursor, 1-phenyl-2-(4-(pyridin-2-yl)phenyl)-1 H -phenanthro[9,10-d]imidazole ( N^CH ), was readily obtained in good yield using Debus-Radziszewski reaction in a way reported to a closely analogous compound [ 34 ] ( Scheme 1 ).…”

Section: Resultsmentioning

confidence: 99%

pH-Responsive N^C-Cyclometalated Iridium(III) Complexes: Synthesis, Photophysical Properties, Computational Results, and Bioimaging Application

et al. 2021

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Herein we report four [Ir(N^C)2(L^L)]n+, n = 0,1 complexes (1–4) containing cyclometallated N^C ligand (N^CH = 1-phenyl-2-(4-(pyridin-2-yl)phenyl)-1H-phenanthro[9,10-d]imidazole) and various bidentate L^L ligands (picolinic acid (1), 2,2′-bipyridine (2), [2,2′-bipyridine]-4,4′-dicarboxylic acid (3), and sodium 4,4′,4″,4‴-(1,2-phenylenebis(phosphanetriyl))tetrabenzenesulfonate (4). The N^CH ligand precursor and iridium complexes 1–4 were synthesized in good yield and characterized using chemical analysis, ESI mass spectrometry, and NMR spectroscopy. The solid-state structure of 2 was also determined by XRD analysis. The complexes display moderate to strong phosphorescence in the 550–670 nm range with the quantum yields up to 30% and lifetimes of the excited state up to 60 µs in deoxygenated solution. Emission properties of 1–4 and N^CH are strongly pH-dependent to give considerable variations in excitation and emission profiles accompanied by changes in emission efficiency and dynamics of the excited state. Density functional theory (DFT) and time-dependent density functional theory (TD DFT) calculations made it possible to assign the nature of emissive excited states in both deprotonated and protonated forms of these molecules. The complexes 3 and 4 internalize into living CHO-K1 cells, localize in cytoplasmic vesicles, primarily in lysosomes and acidified endosomes, and demonstrate relatively low toxicity, showing more than 80% cells viability up to the concentration of 10 µM after 24 h incubation. Phosphorescence lifetime imaging microscopy (PLIM) experiments in these cells display lifetime distribution, the conversion of which into pH values using calibration curves gives the magnitudes of this parameter compatible with the physiologically relevant interval of the cell compartments pH.

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Luminescent organic dyes containing a phenanthro[9,10-D]imidazole core and [Ir(N^C)(N^N)]⁺ complexes based on the cyclometalating and diimine ligands of this type

Abstract: New N^N and N^C luminescent ligands with solvatochromic behavior and their iridium complexes were synthesized, characterized and investigated.

Cited by 21 publications

References 47 publications

Biocompatible Ir(III) Complexes as Oxygen Sensors for Phosphorescence Lifetime Imaging

Biocompatible Ir(III) Complexes as Oxygen Sensors for Phosphorescence Lifetime Imaging

A Panchromatic Cyclometalated Iridium Dye Based on 2-Thienyl-Perimidine

pH-Responsive N^C-Cyclometalated Iridium(III) Complexes: Synthesis, Photophysical Properties, Computational Results, and Bioimaging Application

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Luminescent organic dyes containing a phenanthro[9,10-D]imidazole core and [Ir(N^C)(N^N)]+ complexes based on the cyclometalating and diimine ligands of this type

Abstract: New N^N and N^C luminescent ligands with solvatochromic behavior and their iridium complexes were synthesized, characterized and investigated.

Cited by 21 publications

References 47 publications

Biocompatible Ir(III) Complexes as Oxygen Sensors for Phosphorescence Lifetime Imaging

Biocompatible Ir(III) Complexes as Oxygen Sensors for Phosphorescence Lifetime Imaging

A Panchromatic Cyclometalated Iridium Dye Based on 2-Thienyl-Perimidine

pH-Responsive N^C-Cyclometalated Iridium(III) Complexes: Synthesis, Photophysical Properties, Computational Results, and Bioimaging Application

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Luminescent organic dyes containing a phenanthro[9,10-D]imidazole core and [Ir(N^C)(N^N)]⁺ complexes based on the cyclometalating and diimine ligands of this type