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81.
Abstract— Three covalently-linked porphyrin hybrid dimers were synthesized, each containing a metallotetraarylporphyrin [Zn(II), Cu(II), or Ni(II)], and a free base tetraarylporphyrin. Transfer of singlet excitation energy from the metalloporphyrin center to the free base porphyrin center was determined by measuring fluorescence properties. The Zn hybrid dimer displayed excellent intramolecular transfer of energy ( 85%) from the excited singlet state of the Zn(II) chromophore to the free base chromophore. No evidence for such transfer of the excited singlet state energy was found in the Ni(II) or Cu(II) analogues. From our experimental data, the fluorescence quantum yield of the Zn hybrid dimer was the same as for the free base monomer porphyrin (0.11; Seybold and Gouterman, 1969). Thus, the covalent attachment of another fluorescent porphyrin center effectively doubled the antenna size without decreasing the quantum yield even though the fluorescence quantum yield of the Zn(II) containing monomer was substantially less (0.03, according to Seybold and Gouterman, 1969) than that of the free base porphyrin. The donor-acceptor distance and the rate constant for energy transfer were calculated using the Forster equation. Assuming random orientation, a donor-acceptor distance of 15 Å was calculated with an associated rate constant (kci) for energy transfer of 1.9 ± 109 s–1. 相似文献
82.
Busby M Gabrielsson A Matousek P Towrie M Di Bilio AJ Gray HB Vlcek A 《Inorganic chemistry》2004,43(16):4994-5002
The nature and dynamics of the lowest excited states of fac-[Re(I)(L)(CO)(3)(phen)](+) and fac-[Re(I)(L)(CO)(3)(5-NO(2)-phen)](+) [L = Cl(-), 4-ethyl-pyridine (4-Etpy), imidazole (imH); phen = 1,10-phenanthroline] have been investigated by picosecond visible and IR transient absorption spectroscopy in aqueous (L = imH), acetonitrile (L = 4-Etpy, imH), and MeOH (L = imH) solutions. The phen complexes have long-lived Re(I) --> phen (3)MLCT excited states, characterized by CO stretching frequencies that are upshifted relative to their ground-state values and by widely split IR bands due to the out-of-phase A'(2) and A"nu(CO) vibrations. The lowest excited states of the 5-NO(2)-phen complexes also have (3)MLCT character; the larger upward nu(CO) shifts accord with much more extensive charge transfer from the Re(I)(CO)(3) unit to 5-NO(2)-phen in these states. Transient visible absorption spectra indicate that the excited electron is delocalized over the 5-NO(2)-phen ligand, which acquires radical anionic character. Similarly, involvement of the -NO(2) group in the Franck-Condon MLCT transition is manifested by the presence of an enhanced nu(NO(2)) band in the preresonance Raman spectrum of [Re(I)(4-Etpy)(CO)(3)(5-NO(2)-phen)](+). The Re(I) --> 5-NO(2)-phen (3)MLCT excited states are very short-lived: 7.6, 170, and 43 ps for L = Cl(-), 4-Etpy, and imH, respectively, in CH(3)CN solutions. The (3)MLCT excited state of [Re(I)(imH)(CO)(3)(5-NO(2)-phen)](+) is even shorter-lived in MeOH (15 ps) and H(2)O (1.3 ps). In addition to (3)MLCT, excitation of [Re(I)(imH)(CO)(3)(5-NO(2)-phen)](+) populates a (3)LLCT (imH --> 5-NO(2)-phen) excited state. Most of the (3)LLCT population decays to the ground state (time constants of 19 (H(2)O), 50 (MeOH), and 72 ps (CH(3)CN)); in a small fraction, however, deprotonation of the imH.+ ligand occurs, producing a long-lived species, [Re(I)(im.)(CO)(3)(5-NO(2)-phen).-]+. 相似文献
83.
Pericàs MA Puigjaner C Riera A Vidal-Ferran A Gómez M Jiménez F Muller G Rocamora M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(18):4164-4178
New families of enantiopure bis(oxazolines) with 4,5-trans (5 a-g) or 4,5-cis (6 c) stereochemistry at the individual rings have been prepared in high yield. Their eta(3)-allyl palladium complexes (8 a-g, 9 c and 10) have been used as catalytic precursors in allylic alkylation reactions with excellent enantioselectivities (up to 96 %) for the trans oxazoline derivatives, while Pd/6 c system was inactive. NMR studies on palladium eta(3)-1,3-diphenylallyl intermediates (11 a, c and e) showed the presence of syn/syn- and syn/anti-allyl isomers in solution; this resembles the first example of eta(3)-eta(1)-eta(3) isomerism in Pd allylic complexes containing bis(oxazolines) derived from malonic acid. 相似文献
84.
A new interpretation of the electronic spectroscopy, photochemistry, and photophysics of group 6 metal cis-tetracarbonyls [M(CO)(4)L(2)] is proposed, that is based on an interplay between M --> L and M --> CO MLCT excited states. TD-DFT and resonance Raman spectroscopy show that the lowest allowed electronic transition of [W(CO)(4)(en)] (en = 1,2-ethylenediamine) has a W(CO(eq))(2) --> CO(ax) charge-transfer character, whereby the electron density is transferred from the equatorial W(CO(eq))(2) moiety to pi orbitals of the axial CO ligands, with a net decrease of electron density on the W atom. The lowest, emissive excited state of [W(CO)(4)(en)] was identified as a spin-triplet W(CO(eq))(2) --> CO(ax) CT excited state both computationally and by picosecond time-resolved IR spectroscopy. This state undergoes 1.5 ps vibrational relaxation/solvation and decays to the ground state with a approximately 160 ps lifetime. The nu(CO) wavenumbers and IR intensity pattern calculated by DFT for the triplet W(CO(eq))(2) --> CO(ax) CT excited state match well the experimental time-resolved spectrum. For [W(CO)(4)(R-DAB)] (R-DAB = N,N'-bis-alkyl-1,4-diazabutadiene), the W(CO(eq))(2) --> CO(ax) CT transition follows in energy the W --> DAB MLCT transition, and the emissive W(CO(eq))(2) --> CO(ax) CT triplet state occurs just above the manifold of triplet W --> DAB MLCT states. No LF electronic transitions were calculated to occur in a relevant energetic range for either complex. Molecular orbitals of both complexes are highly delocalized. The 5d(W) character is distributed over many molecular orbitals, while neither of them contains a predominant metal-ligand sigma 5d(W) component, contrary to predictions of the traditional ligand-field approach. The important spectroscopic, photochemical, and photophysical roles of M(CO(eq))(2) --> CO(ax) CT excited states and the limited validity of ligand field arguments can be generalized to other mixed-ligand carbonyl complexes. 相似文献
85.
Olga Bakulina Anton Bannykh Ekaterina Levashova Mikhail Krasavin 《Molecules (Basel, Switzerland)》2022,27(12)
Screening of a library of novel N-hydroxylactams amenable by the Castagnoli-Cushman reaction identified four lead compounds that facilitated 55Fe transport into P. aeruginosa cells (one of these synthetic siderophores was found to be as efficient at promoting iron uptake as the natural siderophores pyoverdine, pyochelin or enterobactin). Conjugates of the four lead siderophores with ciprofloxacin were tested for antibacterial activity against P. aeruginosa POA1 (wild type) and the ∆pvdF∆pchA mutant strain. The antibacterial activity was found to be pronounced against the ∆pvdF∆pchA mutant strain grown in CAA medium but not for the POA1 strain. This may be indicative of these compounds being ‘Trojan horse’ antibiotics. Further scrutiny of the mechanism of the antibacterial action of the newly developed conjugates is warranted. 相似文献
86.
87.
Yury L. Karavaev Alexander A. Kilin Anton V. Klekovkin 《Regular and Chaotic Dynamics》2016,21(7-8):918-926
In this paper we describe the results of experimental investigations of the motion of a screwless underwater robot controlled by rotating internal rotors. We present the results of comparison of the trajectories obtained with the results of numerical simulation using the model of an ideal fluid. 相似文献
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