The effect of deuteriation on the emission lifetime of inorganic compounds

Browne, Wesley R.; Vos, Johannes G.

doi:10.1016/s0010-8545(01)00366-6

Cited by 80 publications

(102 citation statements)

References 120 publications

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“…On the basis of these results the extension in emission lifetime and increase in emission intensity were assigned as being due to the increased rigidity of the Ru(II) complex and the consequent reduction in the contribution of vibrational modes to the deactivation of the 3 MLCT excited state. 18 In contrast to Nd 3+ , Tb 3+ and Gd 3+ , for Eu 3+ , a decrease in emission intensity of the [Ru(bipy) 3 ] 2+ core was observed. However, a simultaneous sensitisation in the Eu(III) emission was not observed.…”

Section: 47mentioning

confidence: 86%

“…More recently other techniques such as ESR 19 spectroscopy, and, increasingly, computational methods have been applied. In addition, other strategies such as deuteration, both of solvent and ligand, 18 and acid-base 20 behaviour have proven useful in elucidating electronic structure. ) of the Raman scattering from vibrational modes of the chromophore can occur.…”

Section: Experimental Methods For the Investigation Of The Electronicmentioning

confidence: 99%

“…With the exception of lanthanide-based systems, where essentially pure metal-centred (MC) excited states are involved, this is rarely the case, and indeed significant mixing of metal and ligand orbitals occurs in the majority of transition metal based systems. 18 In Fig. 5 the components of a typical transition metal based donor-acceptor system are illustrated.…”

Section: What Is the Donor-acceptor Separation?mentioning

confidence: 99%

“…18 Many studies have been reported for organic systems but application of the strategy in inorganic chemistry has been more limited. It has been demonstrated, however, that deuteration of specific ligands in heteroleptic compounds can assist in determining the nature of the emitting state.…”

Section: Isotopic Labellingmentioning

confidence: 99%

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Elucidating Excited State Electronic Structure and Intercomponent Interactions in Multicomponent and Supramolecular Systems

et al. 2005

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Rational design of supramolecular systems for application in photonic devices requires a clear understanding of both the mechanism of energy and electron transfer processes and how these processes can be manipulated. Central to achieving these goals is a detailed picture of their electronic structure and of the interaction between the constituent components. We review several approaches that have been taken towards gaining such understanding, with particular focus on the physical techniques employed. In the discussion, case studies are introduced to illustrate the key issues under consideration. IntroductionMolecular devices, based on supramolecular (multicomponent) assemblies employing covalent and non-covalent bonds between components, are of increasing interest in the development of molecular electronics and photonic devices. One of the primary goals behind the construction of supramolecular systems is to control the direction and rate of electron and energy transfer processes, both energetically and spatially. Although the energetic characteristics of these systems can be manipulated relatively easily, spatial control, in terms of both direction and rate, of energy and electron transfer can be achieved only when the orbital nature of both ground and excited electronic states is understood. Multinuclear transition metal complexes, such as those based on d 6 polypyridyl complexes (i.e., Re(I), Ru(II), Os(II) Rh(III), Ir(III)) have received considerable attention, both in fundamental studies and for application in molecular photonics. 2 The attraction of these metal compounds arises from the well-defined electrochemical and photophysical properties of their polypyridyl complexes and the extensive synthetic chemistry available, which enables systematic tuning of these properties for particular applications. 3 An additional advantage of employing 2nd and 3rd row transition metal complexes in studying intercomponent interactions lies in the stability of these complexes in different redox states. In consequence, the present tutorial review focuses primarily on metal-centred systems. However, it must be emphasised that the techniques discussed and approaches taken in these studies are not exclusive to metal based systems but can be applied equally well to organic systems. Han Vos, where he used density functional theory to study the electronic structures and Raman spectra of ruthenium complexes. After completing his PhD in 2004, he was appointed as a postdoctoral researcher in the group of P r o f . C i a r a n R e g a n i n University College Dublin. His current research interests involve the application of computational techniques to systems of biological interest.

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Section: 47mentioning

confidence: 86%

Section: Experimental Methods For the Investigation Of The Electronicmentioning

confidence: 99%

Section: What Is the Donor-acceptor Separation?mentioning

confidence: 99%

Section: Isotopic Labellingmentioning

confidence: 99%

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Elucidating Excited State Electronic Structure and Intercomponent Interactions in Multicomponent and Supramolecular Systems

et al. 2005

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“…This will affect the (averaged over nuclear vibrations) molecular energy levels [18], as well as the values of derivative coupling elements responsible for nonadiabatic transitions [13,15,27]. Isotopic substitution has been used to increase the excited state lifetime of organic molecules and transition metal complexes used in organic light-emitting diodes (OLED), in order to increase the luminescence yield by reducing the rate of nonradiative decay, due to vibronic coupling [28][29][30][31], but studies of the isotopic effect on the performance of photoelectrochemical cells are almost non-existent. We have recently estimated the effect of deuteration of tetracyanoethylene (TCNE), tetracyanoquinodimethane (TCNQ) and tetracyanoanthraquinodimethane (TCNAQ) on the geminate recombination in cells utilizing interfacial charge transfer bands (so-called direct injection cells) [13].…”

Section: Introductionmentioning

confidence: 99%

Effect of Isotopic Substitution on Elementary Processes in Dye-Sensitized Solar Cells: Deuterated Amino-Phenyl Acid Dyes on TiO2

2013

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Abstract:We present the first computational study of the effects of isotopic substitution on the operation of dye-sensitized solar cells. Ab initio molecular dynamics is used to study the effect of deuteration on light absorption, dye adsorption dynamics, the averaged over vibrations driving force to injection (∆G i ) and regeneration (∆G r ), as well as on promotion of electron back-donation in dyes NK1 (2E,4E-2-cyano-5-(4-dimethylaminophenyl)penta-2,4-dienoic acid) and NK7 (2E,4E-2-cyano-5-(4-diphenylaminophenyl)penta-2,4-dienoic acid) adsorbed in monodentate molecular and bidentate bridging dissociative configurations on the anatase (101) surface of TiO 2 . Deuteration causes a red shift of the absorption spectrum of the dye/TiO 2 complex by about 5% (dozens of nm), which can noticeably affect the overlap with the solar spectrum in real cells. The dynamics effect on the driving force to injection and recombination (the difference between the averaged <∆G i,r > and ∆G i,r equil at the equilibrium configuration) is strong, yet there is surprisingly little isotopic effect: the average driving force to injection <∆G i > and to regeneration <∆G r > changes by only about 10 meV upon deuteration. The nuclear dynamics enhance recombination to the dye ground state due to the approach of the electron-donating group OPEN ACCESSComputation 2013, 1 2 to TiO 2 , yet this effect is similar for deuterated and non-deuterated dyes. We conclude that the nuclear dynamics of the C-H(D) bonds, mostly affected by deuteration, might not be important for the operation of photoelectrochemical cells based on organic dyes. As the expectation value of the ground state energy is higher than its optimum geometry value (by up to 0.1 eV in the present case), nuclear motions will affect dye regeneration by recently proposed redox shuttle-dye combinations operating at low driving forces.

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The Electronic Structure of Organic Semiconductors

2015

Electronic Processes in Organic Semiconductors

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The effect of deuteriation on the emission lifetime of inorganic compounds

Cited by 80 publications

References 120 publications

Elucidating Excited State Electronic Structure and Intercomponent Interactions in Multicomponent and Supramolecular Systems

Elucidating Excited State Electronic Structure and Intercomponent Interactions in Multicomponent and Supramolecular Systems

Effect of Isotopic Substitution on Elementary Processes in Dye-Sensitized Solar Cells: Deuterated Amino-Phenyl Acid Dyes on TiO2

The Electronic Structure of Organic Semiconductors

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