Gallium(III) Corroles

Weaver, Jeremy J.; Sorasaenee, Karn; Sheikh, Mayra; Goldschmidt, Ruth; Tkachenko, Elena; Gross, Zeev; Gray, Harry B.

doi:10.1002/chin.200510276

Cited by 3 publications

(6 citation statements)

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“…The energy gap measured between the 0-0 peaks observed in the absorption spectrum and the high-energy emission is nil, indicating that this emission is indeed fluorescent. The presence of fluorescence (and phosphorescence) for 3 is perfectly consistent with the recently reported related Ga(Corro1e) complexes, which exhibit strong fluorescence at room temperature in fluid solution (24,25). In addition, weaker phosphorescence is depicted at 739 nm based on a larger energy gap between the 0-0 peak observed in the Q-bands and this emission maximum (4100 cm?).…”

Section: Energy Diagramsupporting

confidence: 90%

“…For example, the 0‐0 Q bands are located at 578, 589 and 554 nm for Cu(TPP), Zn(TPP) and Pd(TPP) (in benzene), respectively (15). This is also true for the 5,10,15‐tris(pentafluoro‐phenyl)corrole absorbing at 602 nm (CH 2 Cl 2 ) (23), whereas the corresponding Ga III complex (as a pyridine adduct in CH 2 Cl 2 ) exhibits a 0‐0 Q band at 594 nm (24, 25).…”

Section: Resultsmentioning

confidence: 83%

“…The τ e and φ e data are indicated in Table 2. In comparison with the Ga(Corrole) strong emitters (24, 25), 3 is a weak emitter. Both τ F and φ F are two orders of magnitude smaller than that reported for the gallium species and free bases of corrole (22), even at 77 K. τ p could not be measured because of the weakness of the phosphorescence intensity in our system.…”

Section: Resultsmentioning

confidence: 93%

“…and 554 nm for Cu(TPP), Zn(TPP) and Pd(TPP) (in benzene), respectively (15). This is also true for the 5,10,15-tris(pentafluoro-pheny1)corrole absorbing at 602 nm (CH2C12) (23), whereas the corresponding Ga"' complex (as a pyridine adduct in CH2C12) exhibits a 0-0 Q band at 594 nm (24,25). UV-vis spectra of 1-3 in 2MeTHF at 77 K. The addition of 10 nm to the absorption spectrum of 3 (Fig.…”

Section: Energy Diagrammentioning

confidence: 87%

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Photophysical Properties of a Rhodium Tetraphenylporphyrin-tin Corrole Dyad. The First Example of a Through Metal–Metal Bond Energy Transfer†

Poulin

Stern

Guilard

et al. 2006

Photochem Photobiol

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The luminescence spectroscopy study and the determination of the photophysical parameters for the M-M'-bonded rhodium meso-tetraphenylporphyrin-tin(2,3,7,13,17,18-hexamethyl-8,12-diethylcorrole) complex, (TPP)Rh-Sn(Me6Et2Cor) 1, was investigated. The emission bands as well as the lifetimes (tau(e)) and the quantum yields (Phi(e); at 77 K using 2MeTHF as solvent) were compared with those of (TPP)RhI 2 (TPP = tetraphenylporphyrin) and (Me6Et2Cor)SnCl 3 (Me6Et2Cor = 2,3,7,13,17,18-hexamethyl-8,12-diethylcorrole) which are the two chemical precursors of 1. The energy diagram has been established from the absorption, fluorescence and phosphorescence spectra. The Rh(TPP) and Sn(Me6Et2Cor) chromophores are the energy donor (D) and acceptor (A), respectively. The total absence of fluorescence in 1 (while fluorescence is observed in the tin derivative 3) indicates efficient excited state deactivation, presumably due to heavy atom effect and intramolecular energy transfer (ET). The large decreases in tau(P) and Phi(P) of the Rh(TPP) chromophore going from 2 to 1 indicate a significant intramolecular ET in the triplet states of 1 with an estimated rate ranging between 10(6) and 10(8) s(-1). Based on the comparison of transfer rates with other related dyads that exhibit similar D-A separations and no M-M' bond, and for which slower through space ET processes (10(2)-10(3) s(-1)) operate, a through M-M' bond ET has been unambiguously assigned to 1.

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Section: Energy Diagramsupporting

confidence: 90%

Section: Resultsmentioning

confidence: 83%

Section: Resultsmentioning

confidence: 93%

Section: Energy Diagrammentioning

confidence: 87%

See 2 more Smart Citations

Photophysical Properties of a Rhodium Tetraphenylporphyrin-tin Corrole Dyad. The First Example of a Through Metal–Metal Bond Energy Transfer†

Poulin

Stern

Guilard

et al. 2006

Photochem Photobiol

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“…In vitro investigations into HSA binding with drugs may provide insight into the pharmacokinetics of the reaction . To date, only a few reports about the binding behavior of corrole with HSA are available . In connection with our previous work on the nuclease activity of metal corrole , we here report the DNA‐binding, HSA interaction and nuclease‐like activity of an iron‐sulfonated corrole Fe–SC (Fig.…”

Section: Introductionmentioning

confidence: 83%

DNA/HSA interaction and nuclease activity of an iron(III) amphiphilic sulfonated corrole

et al. 2015

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The DNA binding of amphiphilic iron(III) 2,17-bis(sulfonato)-5,10,15-tris(pentafluorophenyl)corrole complex (Fe-SC) was studied using spectroscopic methods and viscosity measurements. Its nuclease-like activity was examined by using pBR322 DNA as a target. The interaction of Fe-SC with human serum albumin (HSA) in vitro was also examined using multispectroscopic techniques. Experimental results revealed that Fe-SC binds to ct-DNA via an outside binding mode with a binding constant of 1.25 × 10(4) M(-1). This iron corrole also displays good activity during oxidative DNA cleavage by hydrogen peroxide or tert-butyl hydroperoxide oxidants, and high-valent (oxo)iron(V,VI) corrole intermediates may play an important role in DNA cleavage. Fe-SC exhibits much stronger binding affinity to site II than site I of HSA, indicating a selective binding tendency to HSA site II. The HSA conformational change induced by Fe-SC was confirmed by UV/Vis and CD spectroscopy.

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Time-Resolved Electron Paramagnetic Resonance Study of Rhodium(III) Corrole Excited States

et al. 2010

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Photoexcited states of three Rh(III) 5,10,15-tris(pentafluorophenyl)corroles coordinated by different axial ligands; namely, triphenylphosphine P(C(6)H(5))(3) group (1), pyridine C(6)H(5)N group (2), and two pyridine groups (3) were studied by X- and Q-band time-resolved electron paramagnetic resonance (TREPR) in frozen toluene and liquid crystal E-7. Transient mutations were utilized to identify multiplicity of the detected paramagnetic species. The spectra of 1 and 2 were assigned to triplet ((3)pipi*) states, while contributions of triplet ((3)dd and charge transfer (3)CT) and quintet ((5)dd) states were revealed in the spectrum of 3. The results are interpreted in terms of a peculiar nature of transition metal complexes with the unfilled d-shell, where close lying electronic states of different multiplicities may be mixed through configurational, spin-orbit, and vibronic coupling. From the EPR spectra, the spin-orbit coupling constant was estimated to be about 25 cm(-1). It is shown that different axial ligation of complexes shifts the relative energy of the excited states and, consequently, leads to population of different states. Plausible explanations of the effects governing unusual spectral and dynamic parameters of the photoexcited Rh corrole complexes are presented.

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Gallium(III) Corroles

Abstract: Organic chemistry Z 0200Gallium (III) Corroles -[25 refs.]. -(WEAVER, J. J.; SORASAENEE, K.; SHEIKH, M.; GOLDSCHMIDT, R.; TKACHENKO, E.; GROSS, Z.; GRAY, H. B.; J.

Cited by 3 publications

References 1 publication

Photophysical Properties of a Rhodium Tetraphenylporphyrin-tin Corrole Dyad. The First Example of a Through Metal–Metal Bond Energy Transfer†

Photophysical Properties of a Rhodium Tetraphenylporphyrin-tin Corrole Dyad. The First Example of a Through Metal–Metal Bond Energy Transfer†

DNA/HSA interaction and nuclease activity of an iron(III) amphiphilic sulfonated corrole

Time-Resolved Electron Paramagnetic Resonance Study of Rhodium(III) Corrole Excited States

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