Exploitation of Luminescent Organometallic Rhenium(I) and Iridium(III) Complexes in Biological Studies

Lo, Kenneth Kam‐Wing

doi:10.1007/3418_2009_3

Cited by 123 publications

(27 citation statements)

References 75 publications

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“…These charge transfer capabilities have been further confirmed with ab initio calculations [10]. Of particular interest is our ultimate design to prepare fullerene/transition metal sensitizers for solar cells [11][12][13][14][15][16][17].…”

Section: Introductionmentioning

confidence: 60%

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Synthesis and Preliminary Characterization of a PPE-Type Polymer Containing Substituted Fullerenes and Transition Metal Ligation Sites

Basinger

Sullivan

Siemer

et al. 2015

Journal of Chemistry

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A substituted fullerene was incorporated into a PPE-conjugated polymer repeat unit. This subunit was then polymerized via Sonogashira coupling with other repeat units to create polymeric systems approaching 50 repeat units (based on GPC characterization). Bipyridine ligands were incorporated into some of these repeat units to provide sites for transition metal coordination. Photophysical characterization of the absorption and emission properties of these systems shows excited states located on both the fullerene and aromatic backbone of the polymers that exist in a thermally controlled equilibrium. Future work will explore other substituted polyaromatic systems using similar methodologies.

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Section: Introductionmentioning

confidence: 60%

“…The product was purified via medium pressure liquid chromatography (MPLC) on silica. (11). In a 100.0 mL Schlenk flask equipped with a stir bar, 10 (0.2500 g, 0.641 mmol), PdCl 2 (PPh 3 ) 2 (0.0442 g, 0.0632 mmol), and CuI (0.3762 g, 1.976 mmol) were added.…”

Section: Attachment Of Substituted Fullerene 1 To 9 (2)mentioning

confidence: 99%

Synthesis and Preliminary Characterization of a PPE-Type Polymer Containing Substituted Fullerenes and Transition Metal Ligation Sites

Basinger

Sullivan

Siemer

et al. 2015

Journal of Chemistry

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“…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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“…8 Debido a esta riqueza de posibilidades se publicaron un gran número de trabajos en los que se estudiaban las propiedades de estos compuestos, haciendo especial hincapié en su fotoactividad. [9][10][11][12][13][14][15] La mayoría de los trabajos iniciales estaban enfocados al estudio de la luminiscencia de los complejos, a la identificación de los estados emisivos envueltos en el proceso y a la determinación de los procesos de transferencia energética que dependen de la naturaleza del ligando. También se han publicado varias revisiones sobre las diversas aplicaciones de las propiedades fotofísicas de estos compuestos, entre las que destacan su actividad como emisores de luz (OLED) 16 o como fotointerruptores 17,18…”

Section: Luminiscencia Estudios Fotofísicos Y Dispositivos Molecularunclassified

Complejos de Reniotricarbonilo con Amidinos: síntesis, mecanismo y propiedades

Iglesias¹

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2. INTRODUCCIÓN 2.1. El fragmento fac-"Re(CO) 3 " 2.1.1. Luminiscencia, estudios fotofísicos y dispositivos moleculares fotoactivos 1 2.1.2. Química bioorganometálica 1 2.1.3. Reducción de CO 2 1 2.1.4. Electroquímica 1 2.1.5. Enlaces supramoleculares y especies polinucleares, aparatos y aplicaciones 1 2.2. El ligando amidino 2.2.1. El ligando pirazolilamidino 1 2.2.2. Mecanismo de formación del ligando pirazolilamidino 2 2.2.3. Ligandos amidino derivados de nucleobases 2 3. OBJETIVOS 4. RESUMEN DE RESULTADOS 4.1. Estudio del mecanismo de formación del pirazolilamidino 4.2. Estudio de las propiedades fotofísicas de los complejos 4.2.1. Estudios fotofísicos 4 4.2.2. Estudios electroquímicos 4 4.2.3. Cálculos teóricos 4 4.3. Formación de complejos amidino a partir de nucleobases 5. ARTÍCULO 1 Pyrazolylamidino Ligands from Coupling of Acetonitrile and Pyrazoles: a Systematic Study 6. ARTÍCULO 2 Luminescent Rhenium(I) Tricarbonyl Complexes with Pyrazolylamidino Ligands: Photophysical, Electrochemical and Computational Studies 7. ARTÍCULO 3 Amidino Ligands from Coupling 1-Methylcytosine and Nitrile: a New Way to Incorporate Biomolecules to Luminiscent Rhenium(I) Tricarbonyl Complexes 8. DOCTORADO INTERNACIONAL

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Exploitation of Luminescent Organometallic Rhenium(I) and Iridium(III) Complexes in Biological Studies

Cited by 123 publications

References 75 publications

Synthesis and Preliminary Characterization of a PPE-Type Polymer Containing Substituted Fullerenes and Transition Metal Ligation Sites

Synthesis and Preliminary Characterization of a PPE-Type Polymer Containing Substituted Fullerenes and Transition Metal Ligation Sites

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

Complejos de Reniotricarbonilo con Amidinos: síntesis, mecanismo y propiedades

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