Effects of the reaction cavity on metastable optical excitation in ruthenium-sulfur dioxide complexes

Phillips, Anthony E.; Cole, Jacqueline M.; d’Almeida, Thierry; Low, Kian Sing

doi:10.1103/physrevb.82.155118

Cited by 43 publications

(80 citation statements)

References 36 publications

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“…This adds a new perspective to the established practice of using crystal engineering to create a "reaction cavity" for the isomerisation to occur within. 39,40,43,51 To investigate this nding in more detail, it would be interesting to calculate the dielectric constants of other known Ni-NO 2 linkage-isomer systems, and to relate these to the photoconversion yield and/or the presence or absence of thermal-isomerisation pathways. It may perhaps also be of interest to relate the dielectric constant to other properties, such as the optical-absorption prole, and the energy difference between magnetic congurations.…”

Section: Discussionmentioning

confidence: 99%

“…The isomerisation takes place within a large reaction cavity, which allows the ligand binding to be switched without inducing a large stress on the crystal. 39,40,43,51 Furthermore, previous computational modelling 40 and experimental measurements of the transition kinetics 46 both suggest that, to a good approximation, the molecules in the solid behave as isolated units, whose properties and behaviour are inuenced by the dielectric environment of the crystal.…”

Section: Continuum Modelsmentioning

confidence: 96%

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Electronic excitations in molecular solids: bridging theory and experiment

et al. 2015

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As the spatial and temporal resolution accessible to experiment and theory converge, computational chemistry is an increasingly powerful tool for modelling and interpreting spectroscopic data. However, the study of molecular processes, in particular those related to electronic excitations (e.g. photochemistry), frequently pushes quantum-chemical techniques to their limit. The disparity in the level of theory accessible to periodic and molecular calculations presents a significant challenge when modelling molecular crystals, since accurate calculations require a high level of theory to describe the molecular species, but must also take into account the influence of the crystalline environment on their properties. In this article, we briefly review the different classes of quantum-chemical techniques, and present an overview of methods that account for environmental influences with varying levels of approximation. Using a combination of solid-state and molecular calculations, we quantitatively evaluate the performance of implicit-solvent models for the [Ni(Et4dien)(η2-O,ON)(η1-NO2)] linkage-isomer system as a test case. We focus particularly on the accurate reproduction of the energetics of the isomerisation, and on predicting spectroscopic properties to compare with experimental results. This work illustrates how the synergy between periodic and molecular calculations can be exploited for the study of molecular crystals, and forms a basis for the investigation of more challenging phenomena, such as excited-state dynamics, and for further methodological developments.

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Section: Discussionmentioning

confidence: 99%

Section: Continuum Modelsmentioning

confidence: 96%

Electronic excitations in molecular solids: bridging theory and experiment

et al. 2015

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“…The viability of compounds 4 and 7 is similarly questionable since Z'=2 in each case. While there exists one example of a successful photocrystallography study on a molecule with Z'=2, 56 this concerned a long-lived photo-induced species; while the microsecond-lived photo-excited states of these iridium-based complexes imposes significantly higher technical demands.…”

Section: Photo-excited Intramolecular Charge-transfer and Optical Banmentioning

confidence: 99%

Material Profiling for Photocrystallography: Relating Single-Crystal Photophysical and Structural Properties of Luminescent Bis-Cyclometalated Iridium-Based Complexes

Cole

Bowes

Clark

et al. 2013

Crystal Growth & Design

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The photophysical properties of seven luminescent iridium complexes are characterised in their single-crystal form and the photo-activity is related to their molecular structures. Specifically, solid-state optical emission spectra and associated lifetimes are determined from single crystals of iridium complexes containing three bidentate ligands: two variously substituted 2phenylbenzothiazoles and either a 2,4-pentadione (acetylacetone) or 2-pyridinecarboxylic (picolinic) acid. All complexes studied exhibit emissive behaviour in the solid-state which originates from 3 * and metal-to-ligand-charge-transfer (MLCT) electronic transitions; this is supported by density functional theory. Phosphorescence is observed in all cases with microsecond lifetimes, ranging from 0.30-2.4 s at 298K and 1.4-4.0 µs at 100 K. Structureproperty relationships are established which are relevant to the potential solid-state application of this series of luminescent complexes as organic light emitting diodes (OLED) material components. In addition, these materials are assessed for their suitability to time-resolved pump-probe photocrystallography experiments, which will reveal their photo-excited-structure. Accordingly, the design process by which materials are selected, and technical parameters are defined, for a photocrystallography experiment is illustrated. This family of complexes presents a case study for this photocrystallography material profiling. Results show that the time-resolved photo-excited state structure, featuring the MLCT transition is, in principle at least, viable for two of these complexes.

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“…Regardless of the broad application of DFT method in chemistry, few cases addressed linkage isomerism in coordination compounds, and even fewer used the NBO approach …”

Section: Introductionmentioning

confidence: 99%

DFT analysis of the linkage isomerism in penta(ammine)ruthenium(II/III) complexes of benzotriazole: Natural bond orbital method approach and a comprehensive energy decomposition analysis

et al. 2019

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Penta(ammine)ruthenium benzotriazole complexes [RuII/III(NH3)5bta]+/2+ and [RuII/III(NH3)5btaH]2+/3+ (bta and btaH are the deprotonated and neutral form of the triazole ligand, respectively) can exhibit two linkage isomers κN1 and κN2. This system was investigated by density functional theory natural bond orbitals analysis and Su‐Li energy decomposition analysis. Steric, electrostatic, exchange, repulsion, polarization, and dispersion energy components of the total metal–ligand interaction were quantitatively evaluated, and revealed that the overall metal‐triazole ligand is comprised of donor–acceptor interactions like σ‐donation and π‐back‐donation, which favors a specific isomer depending on the oxidation state of the ruthenium and the charge of the ligand. Further, activation energies (ΔG‡) for linkage isomerization reactions were calculated. Results were correlated with experimental chemical–electrochemical data and two plausible mechanisms are discussed. © 2019 Wiley Periodicals, Inc.

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Effects of the reaction cavity on metastable optical excitation in ruthenium-sulfur dioxide complexes

Cited by 43 publications

References 36 publications

Electronic excitations in molecular solids: bridging theory and experiment

Electronic excitations in molecular solids: bridging theory and experiment

Material Profiling for Photocrystallography: Relating Single-Crystal Photophysical and Structural Properties of Luminescent Bis-Cyclometalated Iridium-Based Complexes

DFT analysis of the linkage isomerism in penta(ammine)ruthenium(II/III) complexes of benzotriazole: Natural bond orbital method approach and a comprehensive energy decomposition analysis

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