Long-lived, highly luminescent rhenium(I) complexes as molecular probes: intra- and intermolecular excited-state interactions

Sacksteder, LouAnn.; Lee, Maria; Demas, J. N.; DeGraff, Β. A.

doi:10.1021/ja00071a036

Cited by 225 publications

(158 citation statements)

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“…17 Of note, shorter lifetimes in water compared to acetonitrile can be explained by the greater polarity of water, which stabilizes the 3 MLCT excited state, thus lowering its energy and facilitating nonradiative processes. 53,54 The complex itself can be solubilized in pure water up to 0.79 ± 0.13 mM (25°C). Since some studies have previously noted the loss of the monodentate pyridine ligand in solution for this type of complex, 16,18−20 the stability of [Re(CO) 3 (bipy)(py-alkyne)]-(BF 4 ) in water and human blood plasma was assessed.…”

Section: (Bipy)(py-alkyne)]mentioning

confidence: 99%

Enhanced Cytotoxicity through Conjugation of a “Clickable” Luminescent Re(I) Complex to a Cell-Penetrating Lipopeptide

Leonidova

Pierroz

Adams

et al. 2014

ACS Med. Chem. Lett.

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Re(I) tricarbonyl polypyridine-based complexes are particularly attractive metal complexes in the field of inorganic chemical biology due to their luminescent properties, ease of conjugation to targeting biomolecules, and the possibility to prepare their "hot" 99m Tc analogues for radioimaging. In this study, we prepared and characterized a novel, "clickable" complex, [Re(2,2′-bipyridine)(3-ethynylpyridine)(CO) 3 ](BF 4 ) ([Re(CO) 3 (bipy)(pyalkyne)](BF 4 )), exhibiting the characteristic luminescent properties and moderate cytotoxicity of this general class of compound. Using Cu(I)-catalyzed "click" chemistry, the complex was efficiently attached to a lipidated peptide known to increase cell permeability, namely, the myristoylated HIV-1 Tat peptide (myr-Tat), to give Re-myr-Tat. Fluorescence microscopy localization in human cervical cancer cells (HeLa) confirmed enhanced cellular uptake of Re-myr-Tat compared with [Re(CO) 3 (bipy)(py-alkyne)](BF 4 ), and cytotoxicity studies showed that this resulted in an increase in potency to a level comparable with cisplatin (13.0 ± 2.0 μM).

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Section: (Bipy)(py-alkyne)]mentioning

confidence: 99%

Enhanced Cytotoxicity through Conjugation of a “Clickable” Luminescent Re(I) Complex to a Cell-Penetrating Lipopeptide

Leonidova

Pierroz

Adams

et al. 2014

ACS Med. Chem. Lett.

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“…These values combined with fluorescence data and singlet oxygen quantum yield production fit the energy balance of eq. (6) [24,25]: E a = Φ em E em + α E a + Φ st E st (6) where E em is the "0-0" luminescence energy, E a is the molar energy of the laser pulse (hc/λ exc ), E st is the molar energy content of the species formed with a quantum yield Φ st which stores energy for a time longer than the heat integration time and decays with a lifetime τ. When singlet oxygen acts as storing species, the corresponding values for this species are Φ st = Φ Δ and τ = τ Δ .…”

Section: Singlet Oxygen Generation and Lioas Experimentsmentioning

confidence: 99%

“…The accessible excited states, Re(CO) 3 to αligand charge transfer (LLCT), and/or intraligand (IL) excited states, are generally involved with their observed luminescence at room temperature. Due to the fact that they are thermally and photo-chemically stable as well as rich in their excited-state behavior and redox chemistry these complexes have been used in broad research areas such as electron transfer studies [1], solar energy conversion [2][3][4], catalysis [5], as luminescent sensors [6][7][8], and as labeling reagents and non-covalent probes for biomolecules and ions [9][10][11]. For instance, biochemical applications based on the formation of adducts between these rhe nium complexes and biomolecules like DNA have emerged [12,13].…”

Section: Introductionmentioning

confidence: 99%

Solvent effects on the photophysical properties of Bu4N[(4,4′-bpy)Re(CO)3(bpy-5,5′-diCOO)] complex. A combined experimental and computational study

Saavedra

Ragone

Franca

et al. 2016

Journal of Organometallic Chemistry

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The photophysical properties of the complex Bu 4 N[(4,4′-bpy)Re(CO) 3 (bpy-5,5′-diCOO)] were studied in protic and aprotic media with the aid of steady-state and time-resolved techniques and TD-DFT calculations. The absorption spectrum as well as the steady state and time resolved luminescence of the Re(I) complex display a marked solvent effect. The highest and lowest energy absorption bands experience a bathochromic shift as the polarity of the solvent decreases. In addition, the lowest energy band broadens. Two luminescence bands were observed around 430 and 600 nm in protic organic solvents like alcohols. The high energy emission is observed solely in aqueous solutions, while in aprotic solvents only the low energy luminescence is detected. TD-DFT calculations allowed us to identify the main electronic transitions in the low energy region as 1 MLLCT Re(CO) 3 → 4,4′-bpy and 1 MLLCT Re(CO) 3 → bpy-5,5′-diCOO . The simulated absorption spectra of the Re(I) complex in H 2 O, protic (EtOH, MeOH) and aprotic (CHCl 3 , CH 2 Cl 2 , CH 3 CN) organic solvents follow the experimental absorption spectra with reasonable accuracy both in position and relative intensities. The magnitude of the calculated dipole moment (μ) increases with the dielectric constant of the solvent (ε r ). Besides, the energy of 1 MLLCT Re(CO) 3 → 4,4′-bpy also increases with ε r . However, the energy of the 1 MLLCT Re(CO) 3 → bpy-5,5′-diCOO transition is rather insensitive to ε r . This disparity is attributed to the fact that the 1 MLLCT Re(CO) 3 → 4,4′-bpy transition is nearly parallel to the orientation of μ while the 1 MLLCT Re(CO) 3 → bpy-5,5′-diCOO transition is almost perpendicular to it. Unrestricted TDFT calculations were successfully applied to the triplet species. It is observed that in the triplet state the Re N distances are shortened while Re C distances are elongated relative to the ground state. The calculated emission energy by TD-DFT and/or Δ(SCF) methods was compared to the experimental emission maximum in chloroform. All the experimental results as well as the theoretical calculations indicate that solvent effects on the steady state and time resolved luminescence of the Re(I) complex can be accounted by the coexistence of 3 MLLCT Re(CO) 3 → 4,4′-bpy , 3 MLLCT Re(CO) 3 → bpy-5,5′-diCOO and 1 IL excited states.

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“…Carbonyl bipyridine Re(I) complexes and their derivatives, such as Re-Phen exhibit characteristic long-lived metal-to-ligand charge transfer (MLCT) excited states [14]. They have highly desirable properties including microsecond lifetimes in solution, intense visible absorption and phosphorescence emission, good redox chemistry and high stability [14,15]. The PV devices using Re(I) complexes as electron acceptors have been demonstrated [10].…”

Section: Introductionmentioning

confidence: 99%

Rhenium(I) complex as an electron acceptor in a photovoltaic device

Yue

Fan

et al. 2007

Journal of Alloys and Compounds

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Long-lived, highly luminescent rhenium(I) complexes as molecular probes: intra- and intermolecular excited-state interactions

Cited by 225 publications

References 1 publication

Enhanced Cytotoxicity through Conjugation of a “Clickable” Luminescent Re(I) Complex to a Cell-Penetrating Lipopeptide

Enhanced Cytotoxicity through Conjugation of a “Clickable” Luminescent Re(I) Complex to a Cell-Penetrating Lipopeptide

Solvent effects on the photophysical properties of Bu4N[(4,4′-bpy)Re(CO)3(bpy-5,5′-diCOO)] complex. A combined experimental and computational study

Rhenium(I) complex as an electron acceptor in a photovoltaic device

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