A5033251610- Photochemistry and Electron Transfer Studies
- Metal complexes synthesis and properties
- CO2 Reduction Techniques and Catalysts
- Electrochemical Analysis and Applications
- Magnetism in coordination complexes
- Porphyrin and Phthalocyanine Chemistry
- Lanthanide and Transition Metal Complexes
- Inorganic and Organometallic Chemistry
- Metal-Catalyzed Oxygenation Mechanisms
- Organometallic Complex Synthesis and Catalysis
- Molecular Junctions and Nanostructures
- Radical Photochemical Reactions
- Solid-state spectroscopy and crystallography
- Organic and Molecular Conductors Research
- X-ray Diffraction in Crystallography
- Crystallization and Solubility Studies
- Spectroscopy and Quantum Chemical Studies
- Oxidative Organic Chemistry Reactions
- Catalysis and Oxidation Reactions
- Free Radicals and Antioxidants
- Advanced Chemical Physics Studies
- Photosynthetic Processes and Mechanisms
- Molecular Sensors and Ion Detection
- Analytical Chemistry and Sensors
- Photoreceptor and optogenetics research
Czech Academy of Sciences, J. Heyrovský Institute of Physical Chemistry
2016-2025
Queen Mary University of London
2016-2025
California Institute of Technology
2004-2011
École Polytechnique Fédérale de Lausanne
2008-2010
Paul Scherrer Institute
2010
Czech Academy of Sciences
1977-2009
Rutherford Appleton Laboratory
1999-2009
Cornell University
2006-2009
Universidad de Londres
2009
Science and Technology Facilities Council
2008
Energy flow in biological structures often requires submillisecond charge transport over long molecular distances. Kinetics modeling suggests that charge-transfer rates can be greatly enhanced by multistep electron tunneling which redox-active amino acid side chains act as intermediate donors or acceptors. We report transient optical and infrared spectroscopic experiments quantify the extent to an intervening tryptophan residue facilitate transfer between distant metal redox centers a mutant...
Ultrafast electronic-vibrational relaxation upon excitation of the singlet charge-transfer b1A' state [Re(L)(CO)3(bpy)] n (L = Cl, Br, I, 0; L 4-Et-pyridine, 1+) in acetonitrile was investigated using femtosecond fluorescence up-conversion technique with polychromatic detection. In addition, energies, characters, and molecular structures emitting states were calculated by TD-DFT. The luminescence is characterized a broad band at very short times, evolves to steady-state phosphorescence...
Femto- to picosecond excited-state dynamics of the complexes [Re(L)(CO)(3)(N,N)](n) (N,N = bpy, phen, 4,7-dimethyl-phen (dmp); L Cl, n 0; imidazole, 1+) were investigated using fluorescence up-conversion, transient absorption in 650-285 nm range (using broad-band UV probe pulses around 300 nm) and time-resolved IR (TRIR) spectroscopy region CO stretching vibrations. Optically populated singlet charge-transfer (CT) state(s) undergo femtosecond intersystem crossing at least two hot triplet...
The ultrafast vibrational−electronic relaxation upon excitation into the singlet 1A2u (dσ*→pσ) excited state of d8−d8 binuclear complex [Pt2(P2O5H2)4]4− has been investigated in different solvents by femtosecond polychromatic fluorescence up-conversion and broadband transient absorption (TA) spectroscopy. Both sets data exhibit clear signatures vibrational wave packet oscillations Pt−Pt stretch vibration with a period 224 fs, that decay on 1−2 ps time scale, intersystem crossing (ISC) 3A2u...
Complexes of the type Re(X)(CO)3(α-diimine) (X = Cl, Br, I; α-diimine bpy, iPr-PyCa, iPr-DAB) exhibit a significant influence X on energies and intensities their lowest-energy electronic transitions. Resonance Raman experiments revealed change in character lowest energy transitions these complexes from Re → (MLCT) to (XLCT) upon going Cl Br. This halide can be explained by different extents mixing dπ(Re) pπ(X) orbitals. All under study are emissive at 80 K glass; bpy also room temperature...
Ultrafast excited-state dynamics of [Re(L)(CO)(3)(bpy)](n) (L = Cl, Br, n 0; L 4-ethyl-pyridine (Etpy), 1+; bpy 2,2'-bipyridine) have been investigated in dimethylformamide (DMF) solution by fluorescence up-conversion (FlUC) and UV-vis transient absorption (TA) with approximately 100 fs time resolution. TA was also measured the [1-ethyl-3-methyl-imidazolium]BF(4) ionic liquid. The complexes show a very broad band at 540-550 nm zero delay, which decays 100-140 (depending on L) intersystem...
Rhenium(bipyridine)(tricarbonyl)(picoline) units have been linked covalently to tetraphenylmetalloporphyrins of magnesium and zinc via an amide bond between the bipyridine one phenyl substituent porphyrin. The resulting complexes, abbreviated as [Re(CO)(3)(Pic)Bpy-MgTPP][OTf] [Re(CO)(3)(Pic)Bpy-ZnTPP][OTf], exhibit no signs electronic interaction Re(CO)(3)(bpy) metalloporphyrin in their ground states. However, emission spectroscopy reveals solvent-dependent quenching porphyrin on irradiation...
The lowest-lying spectral transitions in [ReX(CO)3(bpy)] (X = Cl, Br, I; bpy 2,2′-bipyridine) complexes were calculated by means of spin–orbit time-dependent density functional theory (SO-TD-DFT) and multistate complete active space second-order perturbation (SO-MS-CASPT2). Computational results are compared with absorption spectra measured different solvents used to qualitatively explain the temperature dependence phosphorescence decay parameters that for whole series complexes. Spin–orbit...
Significance The observation of vibrational wave packets allows tracking the pathways energy relaxation in nonadiabatic surface crossing events (bio)molecular systems, such as conical intersections or charge transfer processes. Here, we identify coherence course conversion between electronic excited states different spin a diplatinum complex solution, an example. Retention is due to fact that rate dramatically accelerated acetonitrile solvent strong solvation higher-lying then provide...
ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTExcited State Redox Potentials of Ruthenium Diimine Complexes; Correlations with Ground and Ligand ParametersA. A. Vlcek, Elaine S. Dodsworth, William J. Pietro, B. P. LeverCite this: Inorg. Chem. 1995, 34, 7, 1906–1913Publication Date (Print):March 1, 1995Publication History Published online1 May 2002Published inissue 1 March 1995https://pubs.acs.org/doi/10.1021/ic00111a043https://doi.org/10.1021/ic00111a043research-articleACS PublicationsRequest...
The UV-visible absorption spectra of [Ru(E)(E')(CO)(2)(iPr-DAB)] (E = E' SnPh(3) or Cl; E Cl, CH(3); iPr-DAB N,N'-di-isopropyl-1,4-diaza-1,3-butadiene) are investigated using CASSCF/CASPT2 and TD-DFT calculations on model complexes [Ru(E)(E')(CO)(2)(Me-DAB)] SnH(3) Me-DAB N,N'-dimethyl-1,4-diaza-1,3-butadiene). calculated transition energies oscillator strengths allow an unambiguous assignment the nonhalide [Ru(SnPh(3))(2)(CO)(2)(iPr-DAB)] [Ru(SnPh(3))(Me)(CO)(2)(iPr-DAB)]. agreement between...
Picosecond dynamics of Re → polypyridine 3MLCT excited states [Re(Etpy)(CO)3(dmb)]+ and [Re(Cl)(CO)3(bpy)] were investigated by time-resolved UV−vis, resonance Raman, IR spectroscopy. Raman bands due to NN•- intraligand vibrations the molecules increase with time during first 15−20 ps after excitation. The constant 6 ± 2 was estimated for areas excited-state [Re(Etpy)(CO)3(dmb)]+. growth is accompanied an near-UV transient absorption band at 375 nm, which corresponds a ππ* transition dmb•-...