The electronic spectrum of tris(2,2'-bipyridine)iron(2+) and tris (2,2'-bipyridine)osmium(2+)

Decurtins, Silvio; Felix, F. W.; Ferguson, J.; Guedel, Hans U.; Lüdi, A.

doi:10.1021/ja00532a020

Cited by 115 publications

(57 citation statements)

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“…22). Similar spectra have already been reported in part by other investigators (e. g., [ 161,288,290]). Like in [Ru(bpy)3] 2+ (see Fig.…”

Section: [Os(bpy)~] Z+supporting

confidence: 89%

“…This is even valid, if all d-orbital contributions are neglected. The absorption structures below = 28000 cm -1 (~ 360 nm) down to = 15000 cm -~ (~ 670 nm) are in general agreement assigned to Os5d-bpyrr* ~MLCT and 3MLCT transitions from the singlet ground state [123,126,136,153,154,161,[285][286][287][288][289][290][291][292][293][294][295]. The emission with its peak maximum near 14000 cm -~ (L-715 nm) results -also in general agreement -from a number of low-lying states being largely of 3MLCT character [34-38, 123, 126, 136, 153, 154, 161, 285-295].…”

Section: [Os(bpy)~] Z+mentioning

confidence: 82%

“…These have been explored with regard to many interesting respects (e. g., see [123,136,153,154,161,[284][285][286][287][288][289][290][291][292]). However, reports on well-resolved spectra which display detailed information about the lowest excited states are only rarely found ( [34-38, 83, 92, 98, 104, 126, 293] and [ t44, 192, 294, 295]).…”

Section: [Os(bpy)~] Z+mentioning

confidence: 99%

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Characterization of excited electronic and vibronic states of platinum metal compounds with chelate ligands by highly frequency-resolved and time-resolved spectra

Yersin

Humbs

Strasser

1997

Topics in Current Chemistry

133

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The lowest excited electronic states of triplet character and related vibronic properties are discussed in detail on the basis of highly frequency-resolved and time-resolved emission and excitation spectra of per-protonated, per-deuterated, and partially deuterated [Pt(bpy)2] 2+, [Rh(bpy)3] 3+, [Ru(bpy)3] 2+, and [Os(bpy)3] ~+. Emphasis is placed on the use of the enormous amount of information displayed in well-resolved vibrational satellite structures. For comparison, IR data and Raman spectra are also used. In addition, data are given for [Ru(bpz)Pt(3-thpy) 2, Pt(2-thpy)(CO)(Cl), Pt(2-thpy) 2, Pt(qol)2, Pt(qtl)2. Trends and effects are also addressed, which are related to the amount of metal d-orbital mixing. In particular, we discuss the role of traps and sites in the context of high-resolution, site-selective, and line-narrowed spectra of chromophores doped into matrices; the interplay between states of ligand-centered 3rtrr* and ~MLCT character; localization versus delocalization behavior; radiative decay properties; zero-field splittings; spin-lattice relaxations via direct and Orbach mechanisms; Arrhenius behavior after time delay; Franck-Condon activities and Huang-Rhys factors; Franck-Condon versus Herzberg Teller activities and tunability of these activities under high magnetic fields; isotope marking and deuteration effects; aggregate formation of [Ru(bpy)3]2+; and radiationless energy transfer in neat [Ru(bpy)3](PF6) 2. These effects are in part treated in detail, but the aim is to use easy-to-follow descriptions. In particular, it is emphasized throughout this review that chemical tunability opens fascinating possibilities for controlled variation of physical properties.

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“…22). Similar spectra have already been reported in part by other investigators (e. g., [ 161,288,290]). Like in [Ru(bpy)3] 2+ (see Fig.…”

Section: [Os(bpy)~] Z+supporting

confidence: 89%

Section: [Os(bpy)~] Z+mentioning

confidence: 82%

Section: [Os(bpy)~] Z+mentioning

confidence: 99%

See 1 more Smart Citation

Characterization of excited electronic and vibronic states of platinum metal compounds with chelate ligands by highly frequency-resolved and time-resolved spectra

Yersin

Humbs

Strasser

1997

Topics in Current Chemistry

133

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“…[42] The two low-lying bands are centered around 520 and 350 nm. These two broad bands have been assigned to MLCT transitions involving Fe (3d) orbitals and p * ligand orbitals.…”

Section: Absorption Spectrum: the Optical Absorption Spectrum Of Aquementioning

confidence: 99%

Study of the Light‐Induced Spin Crossover Process of the [Fe^II(bpy)₃]²⁺ Complex

Graaf

Sousa

2010

Chemistry A European J

100

133

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Ab initio calculations have been performed on [Fe(II)(bpy)3](2+) (bpy = bipyridine) to establish the variation of the energy of the electronic states relevant to light-induced excited-state spin trapping as a function of the Fe-ligand distance. Light-induced spin crossover takes place after excitation into the singlet metal-to-ligand charge-transfer (MLCT) band. We found that the corresponding electronic states have their energy minimum in the same region as the low-spin (LS) state and that the energy dependence of the triplet MLCT states are nearly identical to the (1) MLCT states. The high-spin (HS) state is found to cross the MLCT band near the equilibrium geometry of the MLCT states. These findings give additional support to the hypothesis of a fast singlet-triplet interconversion in the MLCT manifold, followed by a (3)MLCT-HS ((5)T2) conversion accompanied by an elongation of the Fe-N distance.

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“…The effect of the spin-orbit interaction on the electronic structure has been studied in detail for the Fe-, Ru-, and Os-tris(bipyridine) series which covers the 3d, 4d, and 5d shells. 12,[45][46][47] Here, we restrict ourselves to the Fe-Ru comparison, but extend the scope to a broader class of dye molecules, i.e., tris(phenanthroline) and OEP in addition to tris(bipyridine).…”

Section: Introductionmentioning

confidence: 99%

Electronic structure of Fe- vs. Ru-based dye molecules

Johnson

Cook

Zegkinoglou

et al. 2013

The Journal of Chemical Physics

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In order to explore whether Ru can be replaced by inexpensive Fe in dye molecules for solar cells, the differences in the electronic structure of Fe-and Ru-based dyes are investigated by X-ray absorption spectroscopy and first-principles calculations. Molecules with the metal in a sixfold, octahedral N cage, such as tris(bipyridines) and tris(phenanthrolines), exhibit a systematic downward shift of the N 1s-to-π * transition when Ru is replaced by Fe. This shift is explained by an extra transfer of negative charge from the metal to the N ligands in the case of Fe, which reduces the binding energy of the N 1s core level. The C 1s-to-π * transitions show the opposite trend, with an increase in the transition energy when replacing Ru by Fe. Molecules with the metal in a fourfold, planar N cage (porphyrins) exhibit a more complex behavior due to a subtle competition between the crystal field, axial ligands, and the 2+ vs. 3+ oxidation states.

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The electronic spectrum of tris(2,2'-bipyridine)iron(2+) and tris (2,2'-bipyridine)osmium(2+)

Cited by 115 publications

References 0 publications

Characterization of excited electronic and vibronic states of platinum metal compounds with chelate ligands by highly frequency-resolved and time-resolved spectra

Characterization of excited electronic and vibronic states of platinum metal compounds with chelate ligands by highly frequency-resolved and time-resolved spectra

Study of the Light‐Induced Spin Crossover Process of the [Fe^II(bpy)₃]²⁺ Complex

Electronic structure of Fe- vs. Ru-based dye molecules

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The electronic spectrum of tris(2,2'-bipyridine)iron(2+) and tris (2,2'-bipyridine)osmium(2+)

Cited by 115 publications

References 0 publications

Characterization of excited electronic and vibronic states of platinum metal compounds with chelate ligands by highly frequency-resolved and time-resolved spectra

Characterization of excited electronic and vibronic states of platinum metal compounds with chelate ligands by highly frequency-resolved and time-resolved spectra

Study of the Light‐Induced Spin Crossover Process of the [FeII(bpy)3]2+ Complex

Electronic structure of Fe- vs. Ru-based dye molecules

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Product

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Study of the Light‐Induced Spin Crossover Process of the [Fe^II(bpy)₃]²⁺ Complex