A new rhenium(i) tricarbonylpolypyridine donor–acceptor complex featuring a long-lived charge-separated excited state

Ziessel, Raymond; Juris, Alberto; Venturi, Margherita

doi:10.1039/a702902k

Cited by 15 publications

(23 citation statements)

References 14 publications

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“…The electronic absorption spectra of all the complexes show an intense absorption at ca. 350−450 nm in dichloromethane at 298 K. With reference to previous spectroscopic work on related rhenium(I) diimine systems, ,,, this absorption band is most likely assigned as the dπ(Re) → π*(bpy) metal-to-ligand charge-transfer (MLCT) transition. The observation of an extinction coefficient on the order of 10 4 dm 3 mol -1 cm -1 for this band, which is much larger than an order of 10 3 dm 3 mol -1 cm -1 commonly observed for rhenium(I) diimine MLCT transition, is suggestive of a spectral assignment of the band as consisting of an admixture of intraligand (IL) π → π* and MLCT character.…”

Section: Resultsmentioning

confidence: 86%

“…The emission spectra exhibit a broad band centered at ca. 490−560 nm, attributed to the triplet MLCT emission, typical of Re(I) diimine complexes. ,,, The emission energies of the complexes at 77 K glass state and in LB films were found to be blue-shifted with respect to that in fluid solution, attributed to the phenomenon of luminescence rigidochromism . Figure shows the emission spectra of fac -[Re(CO) 3 (bpy)(L2)]PF 6 in various media.…”

Section: Resultsmentioning

confidence: 97%

“…Large NLO responses are usually observed in organometallic molecules that possess large charge-transfer character , show, in addition to their chemosensory 11 and optical switching properties,10b interesting NLO responses. 10i,j, …”

Section: Introductionmentioning

confidence: 99%

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Synthesis, Characterization, and Second-Harmonic Generation Studies of Rhenium(I) Surfactant Complexes in Langmuir−Blodgett Films

Yam

Yang

et al. 1999

Organometallics

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A series of rhenium(I) surfactant complexes of general formula fac-[Re(CO) 3 (bpy)(L)]PF 6 (bpy ) 2,2′-bipyridine, L ) 4-(4′-octadecyloxyphenylazo)pyridine (L1), 4-(4′-octadecyloxyphenylstilbazole)pyridine (L2), 4-(4′-octadecyloxyphenylethynyl)pyridine (L3)) were synthesized and characterized, and their photophysical and photochemical properties studied. The X-ray crystal structure of the complex fac-[Re(CO) 3 (bpy)(L1)]PF 6 has been determined. The formation and optical properties of these complexes in Langmuir-Blodgett (LB) films were studied by surface pressure-area (π-A) isotherms and UV-visible and luminescence spectroscopy. Their second-harmonic generation (SHG) behavior has also been investigated. These Re(I) surfactant complexes were shown to exhibit first-order hyperpolarizabilities comparable to, and in some cases slightly higher than, those of their organic analogues.

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Section: Resultsmentioning

confidence: 86%

Section: Resultsmentioning

confidence: 97%

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Synthesis, Characterization, and Second-Harmonic Generation Studies of Rhenium(I) Surfactant Complexes in Langmuir−Blodgett Films

Yam

Yang

et al. 1999

Organometallics

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“…250−325 nm and less intense spin-allowed metal-to-ligand charge-transfer ( 1 MLCT) (dπ(Re) → π*(N−N)) absorption shoulders at ca. 326−408 nm. 16a-f,h,,,− ,− However, it is likely that the absorption shoulders of Ph 2 -phen complexes 3a and 3b at ca. 339 to 344 nm possess some 1 IL character because of the electron-withdrawing phenyl substituents of Ph 2 -phen.…”

Section: Resultsmentioning

confidence: 99%

Luminescent Tricarbonylrhenium(I) Polypyridine Estradiol Conjugates: Synthesis, Crystal Structure, and Photophysical, Electrochemical, and Protein-Binding Properties

Tsang

Zhu

2006

Organometallics

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A series of luminescent tricarbonylrhenium(I) polypyridine estradiol complexes [Re(N-N)(CO) 3 (L)]-(CF 3 SO 3 ) (N-N ) 1,10-phenanthroline (phen), L ) 4-(17R-ethynylestradiolyl)pyridine (py-est) (1a), 4-(N-(6-(4-(17R-ethynylestradiolyl)benzoylamino)hexanoyl)aminomethyl)pyridine (py-C6-est) (1b); N-N ) 3,4,7,8-tetramethyl-1,10-phenanthroline (Me 4 -phen), L ) py-est (2a), py-C6-est (2b); N-N ) 4,7diphenyl-1,10-phenanthroline (Ph 2 -phen), L ) py-est (3a), py-C6-est (3b)) have been synthesized and characterized. The X-ray crystal structure of complex 1a has also been investigated. The photophysical and electrochemical properties of all the complexes have been studied. Upon irradiation, most of the complexes exhibited intense and long-lived triplet metal-to-ligand charge-transfer ( 3 MLCT) (dπ(Re) f π*(N-N)) emission in fluid solutions at 298 K and in low-temperature glass. The excited states of the Me 4 -phen complexes possessed some triplet intraligand 3 IL character. The lipophilicity of all the complexes has been determined by reversed-phase HPLC. In addition, the binding of these complexes to estrogen receptor R has been investigated by emission titrations.

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“…As we will see, the DEAS-bpy ligand is an electron donor, whereas the BPP ligand is an electron acceptor. The simultaneous coordination of BPP and DEAS-bpy on the same metal center gives rise to very interesting donor−acceptor complexes, which form a long-lived charge-separated state following light excitation . The understanding of the electrochemical and photophysical properties of such complexes requires the comparison with the behavior of the free ligands DEAS-bpy and BPP, and of the model [(DEAS-bpy)ReCl] and [(bpy)Re(BPP)] + complexes.…”

Section: Introductionmentioning

confidence: 99%

Intramolecular Photoinduced Electron Transfer in Multicomponent Rhenium(I) Donor−Acceptor Complexes

1998

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The mononuclear [(DEAS-bpy)Re(CO)3(BPP)]+, [(DEAS-bpy)Re(CO)3(BPP-Me)]2+, and [(bpy)Re(CO)3(BPP)]+ and the binuclear [(DEAS-bpy)Re(CO)3(μ-BPP)Re(CO)3(DEAS-bpy)]2+ complexes have been prepared, and their electrochemical and photophysical properties have been investigated (DEAS-bpy = 4,4‘-bis[p-(diethylamino)-α-styryl]-2,2‘-bipyridine, BPP = 1,10-bis(4-pyridyl)-3,8-dimethyl-1,3,5,7,9-decapentaene, bpy = 2,2‘-bipyridine). The electrochemical behavior of these complexes shows that reduction occurs first on the BPP ligand (E ≈ −0.85 V vs SCE) and then on the DEAS-bpy ligand (E ≈ −1.30 V). The site easier to oxidize is on the amines of the DEAS-bpy ligand (E ≈ +0.70 V); other oxidation processes occur at more positive potential on the ligands and on the metal center. The complexes containing both the DEAS-bpy and the BPP ligands phosphoresce in rigid matrix at 77 K from a 3LC state of the DEAS-bpy ligand (λmax ≈ 675 nm, τ > 350 μs); no emission is observed at room temperature in fluid solution, where a long-lived (τ ≈ 4 μs) species is observed through transient absorption measurements. By combining electrochemical and photophysical data, it is concluded that following light excitation a charge-separated state is formed, which is noticeably long-lived compared to that observed in other donor−acceptor complexes in homogeneous solution.

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A new rhenium(i) tricarbonylpolypyridine donor–acceptor complex featuring a long-lived charge-separated excited state

Cited by 15 publications

References 14 publications

Synthesis, Characterization, and Second-Harmonic Generation Studies of Rhenium(I) Surfactant Complexes in Langmuir−Blodgett Films

Synthesis, Characterization, and Second-Harmonic Generation Studies of Rhenium(I) Surfactant Complexes in Langmuir−Blodgett Films

Luminescent Tricarbonylrhenium(I) Polypyridine Estradiol Conjugates: Synthesis, Crystal Structure, and Photophysical, Electrochemical, and Protein-Binding Properties

Intramolecular Photoinduced Electron Transfer in Multicomponent Rhenium(I) Donor−Acceptor Complexes

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