Ru(II) polypyridine complexes: photophysics, photochemistry, eletrochemistry, and chemiluminescence

Juris, Alberto; Balzani, Vincenzo; Barigelletti, F.; Campagna, Sebastiano; Belser, Peter; Zelewsky, Alex von

doi:10.1016/0010-8545(88)80032-8

Cited by 4,756 publications

(4,386 citation statements)

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“…has a spectrum almost identical with that for Ru(bipy) 3 2+ [26][27][28][29] , with a maximum at 449 nm (MLCT transition) and a shoulder at 424 nm. In addition, it exhibits a strong luminescence at approximately the same wavelengths (610 nm) as Ru(bipy) 3 2+ .…”

Section: Uv-vis Absorption and Emission Spectramentioning

confidence: 78%

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Diastereoselective synthesis of coordination compounds: a chiral tripodal ligand based on bipyridine units and its ruthenium(ii) and iron(ii) complexes

et al. 2004

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Section: Uv-vis Absorption and Emission Spectramentioning

confidence: 78%

“…288 (76.6); 452 (13.6) [26][27][28][29] 610 [30] 301 (80. The absorption spectra of the complexes are basically similar to those for other M(tris-…”

Section: Uv-vis Absorption and Emission Spectramentioning

confidence: 99%

Diastereoselective synthesis of coordination compounds: a chiral tripodal ligand based on bipyridine units and its ruthenium(ii) and iron(ii) complexes

et al. 2004

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“…Indeed, such compounds have some favourable features [15][16][17][18][19]: the ligand can be attached to the metal in a controlled manner; binding to DNA is usually accompanied by marked absorbance changes in the UV-vis frequency range and, sometimes, fluorescence emission too, due to excitation of charge transfer transitions. These properties, together with the analysis of the optical and thermal behaviour of DNA in the presence of these metal complexes, provide a convenient handle for monitoring the binding process.…”

Section: Introductionmentioning

confidence: 99%

The interaction of native DNA with Zn(II) and Cu(II) complexes of 5-triethyl ammonium methyl salicylidene orto-phenylendiimine

Silvestri

Barone

Ruisi

et al. 2007

Journal of Inorganic Biochemistry

106

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The interaction of native calf thymus DNA with the Zn(II) and Cu(II) complexes of 5-triethyl ammonium methyl salicylidene ortophenylendiimine (ZnL 2+ and CuL 2+ ), in 1 mM Tris-HCl aqueous solutions at neutral pH, has been monitored as a function of the metal complex-DNA molar ratio by UV absorption spectrophotometry, circular dichroism (CD) and fluorescence spectroscopy. The results support for an intercalative interaction of both ZnL 2+ and CuL 2+ with DNA, showing CuL 2+ an affinity of approximately 10 times higher than ZnL 2+ . In particular, the values of the binding constant, determined by UV spectrophotometric titration, equal to 7.3 · 10 4 and 1.3 · 10 6 M À1 , for ZnL 2+ and CuL 2+ , respectively, indicate the occurrence of a marked interaction with a binding size of about 0.7 in base pairs. The temperature dependence of the absorbance at 258 nm suggests that both complexes strongly increase the DNA melting temperature (Tm) already at metal complex-DNA molar ratios equal to 0.1. As evidenced by the quenching of the fluorescence of ethidium bromide-DNA solutions in the presence of increasing amounts of metal complex, ZnL 2+ and CuL 2+ are able to displace the ethidium cation intercalated into DNA. A tight ZnL 2+ -DNA and CuL 2+ -DNA binding has been also proven by the appearance, in both metal complex-DNA solutions, of a broad induced CD band in the range 350-450 nm. In the case of the CuL 2+ -DNA system, the shape of the CD spectrum, at high CuL 2+ content, is similar to that observed for w-DNA solutions. Such result allowed us to hypothesize that CuL 2+ induces the formation of supramolecular aggregates of DNA in aqueous solutions.

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“…The nature of the first excited state of [Fe(terpyridine) 2 ] 2+ has been reinvestigated. In contrast to previous findings, it is metal-to-ligand charge transfer in nature, thus fitting in the series of the Ru and Os complexes.…”

Section: Introductionmentioning

confidence: 99%

“…

Recently, a report has been published concerning theoretical calculations on the lowest excited states of [M(terpyridine) 2 ] 2+ and [M(4-(4-(t-butyl)phenyl)terpyridine) 2 ] 2+ 2 (M = Fe, Ru, and Os) complexes calculated using the TD-DFT approach [1].

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mentioning

confidence: 99%

Comment on “Theoretical studies on the ground states in [M(terpyridine)2]2+ and [M(4-(4-(t-butyl)phenyl)terpyridine)2]2+ (M=Fe, Ru, Os) and excited states in [Ru(terpyridine)2]2+ using density functional theory”

Wadman¹,

Geer²,

Havenith³

et al. 2008

Journal of Organometallic Chemistry

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a b s t r a c tThe nature of the first excited state of [Fe(terpyridine) 2 ] 2+ has been reinvestigated. In contrast to previous findings, it is metal-to-ligand charge transfer in nature, thus fitting in the series of the Ru and Os complexes.Ó 2008 Elsevier B.V. All rights reserved.Recently, a report has been published concerning theoretical calculations on the lowest excited states of [M(terpyridine) 2 ] 2+ and [M(4-(4-(t-butyl)phenyl)terpyridine) 2 ] 2+ 2 (M = Fe, Ru, and Os) complexes calculated using the TD-DFT approach [1]. A difference was claimed between the character of the lowest transition of [Fe(terpyridine) 2 ] 2+ and that of the other five considered compounds: whereas the iron complex had intraligand (IL) p-p * character, the lowest transitions of the Ru and Os complexes were predominantly metal-to-ligand charge-transfer (MLCT) excitations. In order to gain insight into this remarkable difference [2-3], we have undertaken a computational study at the same level of theory (B3LYP/LANL2-DZ) as the original authors and found that our results for [Fe(terpyridine) 2 ] 2+ differ from those previously reported.Optimisation of the geometry at the B3LYP/LANL2-DZ level [4] resulted in an identical geometry as reported in [1], identified as a local minimum by normal mode analysis. The orbital energies agreed with the reported values within 0.02 eV. Our TD-DFT [5] results also agreed well with those of Zhou et al. (Table 1 and Tables S1-S3), aside from one low-energy transition with zero oscillator strength (f). In line with the previous study, the first electronic transition with non-zero oscillator strength (f = 0.0122) can be assigned to a degenerate HOMO ? LUMO/HOMO ? LUMO+1 pair transition. The energy of this transition (2.59 eV) agrees with the experimental value of 2.25 eV in aqueous solution [3].The difference between our results and the reported study is the nature of the orbitals involved in this transition, on which the assignment of the character of this transition is based. In contrast to the original findings that the HOMO of [Fe(terpyridine) 2 ] 2+ is ligand-based [1], we find that the HOMO is predominantly metalbased (Fig. 1, Fig. S1 and Table S2). Hence, the current calculations demonstrate that this lowest-energy absorption in [Fe(terpyridine) 2 ] 2+ has MLCT character, instead of IL character. These results thus eliminate the reported difference between the Fe complex and its Ru and Os congeners and lead to overall consistency in the set [M(terpyridine) 2 ] 2+ (M = Fe, Ru and Os).The assignment of this transition to a MLCT transition is independent of basis set: enlargement of the basis to the Ahlrichs-pVDZ basis set [6] or to the non-relativistic cc-pVTZ basis for Fe and to the cc-pVDZ basis set [7] for the other atoms gives similar results. The first non-vanishing transition originates from the metal-based HOMO, Table 1, Tables S4-S7 and Figs. S2-S3; the first visible transition still corresponds to a HOMO ? LUMO/HOMO ? LUMO+1 excitation and the HOMO consists mainly of an Fe d-orbita...

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Ru(II) polypyridine complexes: photophysics, photochemistry, eletrochemistry, and chemiluminescence

Cited by 4,756 publications

References 431 publications

Diastereoselective synthesis of coordination compounds: a chiral tripodal ligand based on bipyridine units and its ruthenium(ii) and iron(ii) complexes

Diastereoselective synthesis of coordination compounds: a chiral tripodal ligand based on bipyridine units and its ruthenium(ii) and iron(ii) complexes

The interaction of native DNA with Zn(II) and Cu(II) complexes of 5-triethyl ammonium methyl salicylidene orto-phenylendiimine

Comment on “Theoretical studies on the ground states in [M(terpyridine)2]2+ and [M(4-(4-(t-butyl)phenyl)terpyridine)2]2+ (M=Fe, Ru, Os) and excited states in [Ru(terpyridine)2]2+ using density functional theory”

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