Normal-coordinate analyses of the ground and 3MLCT excited states of tris(bipyridine)ruthenium(II)

Strommen, Dennis P.; Mallick, Prabal Kumar; Danzer, Gerald D.; Lumpkin, Richard S.; Kincaid, James R.

doi:10.1021/j100367a031

Cited by 164 publications

(157 citation statements)

References 9 publications

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“…These IR features are in good agreement with previously assigned values for this organometallic ion 122,123 . Out of the observed vibrational frequencies, the C-C stretching (1,606; 1,570; 1,042 cm .…”

Section: +supporting

confidence: 92%

<em>In Situ</em> SIMS and IR Spectroscopy of Well-defined Surfaces Prepared by Soft Landing of Mass-selected Ions

Johnson

Gunaratne

Laskin

2014

JoVE

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Soft landing of mass-selected ions onto surfaces is a powerful approach for the highly-controlled preparation of materials that are inaccessible using conventional synthesis techniques. Coupling soft landing with in situ characterization using secondary ion mass spectrometry (SIMS) and infrared reflection absorption spectroscopy (IRRAS) enables analysis of well-defined surfaces under clean vacuum conditions. The capabilities of three soft-landing instruments constructed in our laboratory are illustrated for the representative system of surface-bound organometallics prepared by soft landing of mass-selected ruthenium tris(bipyridine) dications, [Ru(bpy) 3 ] 2+ (bpy = bipyridine), onto carboxylic acid terminated self-assembled monolayer surfaces on gold (COOH-SAMs). In situ time-of-flight (TOF)-SIMS provides insight into the reactivity of the soft-landed ions. In addition, the kinetics of charge reduction, neutralization and desorption occurring on the COOH-SAM both during and after ion soft landing are studied using in situ Fourier transform ion cyclotron resonance (FT-ICR)-SIMS measurements. In situ IRRAS experiments provide insight into how the structure of organic ligands surrounding metal centers is perturbed through immobilization of organometallic ions on COOH-SAM surfaces by soft landing. Collectively, the three instruments provide complementary information about the chemical composition, reactivity and structure of well-defined species supported on surfaces. Video LinkThe video component of this article can be found at

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Section: +supporting

confidence: 92%

<em>In Situ</em> SIMS and IR Spectroscopy of Well-defined Surfaces Prepared by Soft Landing of Mass-selected Ions

Johnson

Gunaratne

Laskin

2014

JoVE

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“…It has been established that the mid-IR region of the spectrum of [Ru(bpy) 3 ] 2+ is composed primarily of bpy ring-breathing modes that may be appropriately modeled as (three) single coordinated bipyridines in C 2V symmetry. 55,56 Assuming this is a suitable approximation for this series of substituted-bpy complexes, the ground-state spectra follow a logical progression as dmb is substituted for dea across the series. For example, the strong 1620 cm -1 band in the [Ru(dmb) 3 The complexity that arises due to localization of the excitedstate electron on one ligand in the infrared spectrum (as opposed to resonance Raman) is immediately obvious from an examination of the nanosecond excited-state difference spectra ( Figure 5).…”

Section: Resultsmentioning

confidence: 99%

Static and Time-Resolved Spectroscopic Studies of Low-Symmetry Ru(II) Polypyridyl Complexes

Curtright

McCusker

1999

J. Phys. Chem. A

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The spectroscopic and electrochemical properties of a series of four Ru II polypyridyl complexes are reported. Compounds of the form [Ru(dmb) x (dea) 3-x ] 2+ (x ) 0-3), where dmb is 4,4′-dimethyl-2,2′-bipyridine and dea is 4,4′-bis(diethylamino)-2,2′-bipyridine, have been prepared and studied using static and time-resolved electronic and vibrational spectroscopies as a prelude to femtosecond spectroscopic studies of excited-state dynamics. Static electronic spectra in CH 3 CN solution reveal a systematic shift of the MLCT absorption envelope from a maximum of 458 nm in the case of [Ru(dmb) 3 ] 2+ to 518 nm for [Ru(dea) 3 ] 2+ with successive substitutions of dea for dmb, suggesting a dea-based chromophore as the lowest-energy species. However, analysis of static and time-resolved emission data indicates an energy gap ordering of [Ru(dmb) , at variance with the electronic structures inferred from the absorption spectra. Nanosecond time-resolved electronic absorption and time-resolved step-scan infrared data are used to resolve this apparent conflict and confirm localization of the long-lived 3 MLCT state on dmb in all three complexes where this ligand is present, thus making the dea-based excited state unique to [Ru-(dea) 3 ] 2+ . Electrochemical studies further reveal the origin of this result, where a strong influence of the dea ligand on the oxidative Ru II/III couple, due to π donation from the diethylamino substituent, is observed. The electronic absorption spectra are then reexamined in light of the now well-determined excited-state electronic structure. The results serve to underscore the importance of complete characterization of the electronic structures of transition metal complexes before embarking on ultrafast studies of their excited-state properties.

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“…But we want to mention the analysis carried out by Kincaid and coworkers. 5 ( [106,209]; cf. also to [211]).…”

Section: Vibrational Satellite Structures Of [Ru(bpu 2+mentioning

confidence: 99%

“…In [268][269][270]209] it has been reported, using resonance Raman data of the excited state(s) of [Ru(bpy)~] 2+, that the vibrational energies are shifted relative to those of the electronic ground state. These shifts were interpreted in favor of a relatively strong distortion due to an electron localization in the lowest excited state(s).…”

Section: Strong Ligand-ligand Coupling Via the Metal And Localizationmentioning

confidence: 99%

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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Normal-coordinate analyses of the ground and 3MLCT excited states of tris(bipyridine)ruthenium(II)

Cited by 164 publications

References 9 publications

<em>In Situ</em> SIMS and IR Spectroscopy of Well-defined Surfaces Prepared by Soft Landing of Mass-selected Ions

<em>In Situ</em> SIMS and IR Spectroscopy of Well-defined Surfaces Prepared by Soft Landing of Mass-selected Ions

Static and Time-Resolved Spectroscopic Studies of Low-Symmetry Ru(II) Polypyridyl Complexes

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

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