Luminescence studies of pyridine .alpha.-diimine rhenium(I) tricarbonyl complexes

Sacksteder, LouAnn.; Zipp, Arden P.; Brown, Elizabeth; Streich, Julie; Demas, J. N.; DeGraff, Β. A.

doi:10.1021/ic00346a033

Cited by 310 publications

(263 citation statements)

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“…Such spectral characteristics are typical of fac-tricarbonyl diimine compounds and the assignments were made in comparison to the literature. 1,3,11,13,17,21,22,33,34 The absorption spectrum of trans-bpe (λ max = 290 nm) shows a characteristic intraligand transition (IL) band which is red shifted (λ max = 312 nm) upon protonation. A similar shift is observed upon coordination of trans-bpe to the rhenium tricarbonyl polypyridyl complexes.…”

Section: H Nmr Spectramentioning

confidence: 99%

“…The broad and structureless band in acetonitrile solution at room temperature is typically a 3 MLCT emission of rhenium(I) compounds. 1,3,5,8,11,13,17,21,33,34,38,39 In order to understand the nature of the emissive state, the investigation was also carried out in different media, e.g., PMMA at 298 K and EPA (diethyl ether-isopentaneethanol, 5:5:2) at 77 K, Figure 6.…”

Section: Upon Irradiation Of Fac-[re(co) 3 (Ph 2 Phen)(trans-bpe)]mentioning

confidence: 99%

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Photoinduced isomerization and luminescence of fac-[Re(CO)3(ph2phen)(bpe)]+

Frin

Iha

2006

J. Braz. Chem. Soc.

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Section: H Nmr Spectramentioning

confidence: 99%

Section: Upon Irradiation Of Fac-[re(co) 3 (Ph 2 Phen)(trans-bpe)]mentioning

confidence: 99%

Photoinduced isomerization and luminescence of fac-[Re(CO)3(ph2phen)(bpe)]+

Frin

Iha

2006

J. Braz. Chem. Soc.

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“…34,35 The lowest energy absorption maxima for all four complexes do not vary significantly, which is expected since the MLCT transition should occur from the Re I metal center to the π* orbitals in the 2,2'-bipyridine. The complexes 1 and 4 exhibit MLCT bands broader and slightly red-shifted in relation to those for the complexes 2 and 3.…”

Section: Spectroscopic and Photophysical Characterizationmentioning

confidence: 71%

“…The syntheses of fac-[Re(CO) 3 (2,2-bpy)(L)]PF 6 (Scheme 1) were performed following the procedures described in the literature 34 …”

Section: Synthesismentioning

confidence: 99%

Influence of the Protonatable Site in the Photo-Induced Proton-Coupled Electron Transfer between Rhenium(I) Polypyridyl Complexes and Hydroquinone

Prado¹,

Sousa²,

Machado³

et al. 2016

J. Braz. Chem. Soc.

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In the present work the influence of the distance of the protonatable site of different ancillary ligands to the metal center on the luminescence quenching of Re I polypyridyl complexes by hydroquinone are evaluated by means of experimental and theoretical studies. In these systems, it is expected the occurrence of proton-coupled electron transfer (PCET) reactions upon excitation, which is a key process in solar-to-fuels energy conversion. The series fac-[Re(CO) 3 (2,2-bpy)(L)]PF 6 , L = pyridine, 1,4-pyrazine, 4,4'-bipyridyl, 1,2-bis-(4-pyridyl)ethane were synthesized and the luminescence quenching rate constant (k q ) by hydroquinone in CH 3 CN and 1:1 CH 3 CN/H 2 O were determined by steady-state and lifetime measurements. In bare acetonitrile, the 1,4-pyrazine exhibits the higher k q (3.49 ± 0.02) × 10 9 L mol -1 s -1 among the species investigated, followed by 4,4'-bipyridyl (k q = 2.50 ± 0.02) × 10 9 L mol -1 s -1. In 1:1 CH 3 CN/H 2 O, the k q values for all complexes are very similar evidencing the role of water molecules as proton acceptor following the reductive quenching of the complexes by hydroquinone. In CH 3 CN, the proton release for the solvent is not spontaneous and the higher basicity of the coordinated 1,4-pyrazine and 4,4'-bipyridyl in relation to 1,2-bis-(4-pyridyl)ethane after metal-to-ligand charge transfer (MLCT) excitation contributes to the proton transfer step. These results are corroborated by time-dependent density functional theory (TD-DFT) calculations. Moreover, the low H/D kinetic isotope effect (KIE) in 3:1 CH 3 CN/X 2 O (X = H or D) confirms that the major PCET pathway is the electron transfer followed by proton transfer, but for 1,4-pyrazine and 4,4'-bipyridyl the concerted proton-electron transfer seems to play a role at high hydroquinone concentrations.

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“…2,29-Bipyridyl(tricarbonyl)rhenium(I) chloride was synthesized according to the literature procedure 11) . Polystyrene-block-poly(4-vinylpyridine) (PS-b-PVP) was synthesized by anionic polymerization under high vacuum (10 -6 mbar) using sec-butyllithium as the initiator and THF as the solvent 12) .…”

Section: Methodsmentioning

confidence: 99%

Polymer aggregates formed by polystyrene-block-poly(4-vinyl-pyridine) functionalized with rhenium(I) 2,2′-bipyridyl complexes

Hou

Chan

1999

Macromol. Rapid Commun.

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SUMMARY: Some metal containing block copolymers derived from polystyrene-block-poly(4-vinylpyridine) were synthesized. The complexation was achieved by reacting the poly(4-vinylpyridine) block with 2,29-bipyridyl(tricarbonyl)rhenium(I) chloride in the presence of silver perchlorate. The resulting polymer metal complexes are able to form micelles in different solvent systems. The morphologies were studied by transmission electron microscopy, and the structure of the micelles was found to be solvent dependent.

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Luminescence studies of pyridine .alpha.-diimine rhenium(I) tricarbonyl complexes

Cited by 310 publications

References 0 publications

Photoinduced isomerization and luminescence of fac-[Re(CO)3(ph2phen)(bpe)]+

Photoinduced isomerization and luminescence of fac-[Re(CO)3(ph2phen)(bpe)]+

Influence of the Protonatable Site in the Photo-Induced Proton-Coupled Electron Transfer between Rhenium(I) Polypyridyl Complexes and Hydroquinone

Polymer aggregates formed by polystyrene-block-poly(4-vinyl-pyridine) functionalized with rhenium(I) 2,2′-bipyridyl complexes

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