Using computational chemistry to design Ru photosensitizers with directional charge transfer

Jäger, Michael; Freitag, Leon; González, Leticia

doi:10.1016/j.ccr.2015.03.019

Cited by 63 publications

(102 citation statements)

References 222 publications

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“…The calculated absorption maximum is obtained at 2.96 eV,w hich is in reasonable agreement with the experimental value of 2.79 eV (i.e., l = 445 nm) measured in acetonitrile. [47][48][49]), showing that the B3LYP XC functional provides an adequate reproductiono ft he excited-state energies, whereas XC functionals with larger percentage of exact exchange werep rovent ob elessaccurate for RuPdCl 2 . [47][48][49]), showing that the B3LYP XC functional provides an adequate reproductiono ft he excited-state energies, whereas XC functionals with larger percentage of exact exchange werep rovent ob elessaccurate for RuPdCl 2 .…”

Section: Excited States Involved In the Initial Photoactivationmentioning

confidence: 98%

“…[8] This is at ypical ac-curacy for TD-DFT calculations on ruthenium complexes (see, e.g.,R efs. [47][48][49]), showing that the B3LYP XC functional provides an adequate reproductiono ft he excited-state energies, whereas XC functionals with larger percentage of exact exchange werep rovent ob elessaccurate for RuPdCl 2 . [11] The main goal of this work is to unravel the possible excited-state relaxation channels populated upon excitation in the longerw avelength range of the absorption spectrum (i.e., around l = 500 nm).…”

Section: Excited States Involved In the Initial Photoactivationmentioning

confidence: 98%

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Theoretical Investigation of the Electron‐Transfer Dynamics and Photodegradation Pathways in a Hydrogen‐Evolving Ruthenium–Palladium Photocatalyst

Staniszewska

Kupfer

Guthmuller

2018

Chemistry A European J

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Time-dependent density functional theory calculations combined with the Marcus theory of electron transfer (ET) were applied on the molecular photocatalyst [(tbbpy) Ru(tpphz)PdCl ] in order to elucidate the light-induced relaxation pathways populated upon excitation in the longer wavelength range of its absorption spectrum. The computational results show that after the initial excitation, metal (Ru) to ligand (tpphz) charge transfer (MLCT) triplet states are energetically accessible, but that an ET toward the catalytic center (PdCl ) from these states is a slow process, with estimated time constants above 1 ns. Instead, the calculations predict that low-lying Pd-centered states are efficiently populated-associated to an energy transfer toward the catalytic center. Thus, it is postulated that these states lead to the dissociation of a Cl and are consequently responsible for the experimentally observed degradation of the catalytic center. Following dissociation, it is shown that the ET rates from the MLCT states to the charge separated states are significantly increased (i.e. 10 -10 times larger). This demonstrates that alteration of the catalytic center generates efficient charge separation.

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Section: Excited States Involved In the Initial Photoactivationmentioning

confidence: 98%

Section: Excited States Involved In the Initial Photoactivationmentioning

confidence: 98%

Theoretical Investigation of the Electron‐Transfer Dynamics and Photodegradation Pathways in a Hydrogen‐Evolving Ruthenium–Palladium Photocatalyst

Staniszewska

Kupfer

Guthmuller

2018

Chemistry A European J

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“…Due to these properties, various classes of TMCs are actively employed, or show high potential, for a large number of innovative technological applications [1]. They are used in devices which convert solar energy, either directly to electrical current in dye-sensitized solar cells [2][3][4][5], to chemical energy of fuels in arti cial photosynthesis [6,7], or to complex chemicals in TMC-based photocatalysis [8][9][10]. Furthermore, TMCs are useful in photodynamic therapy [11][12][13], where light activates therapeutically bene cial chemical reactions that initiate apoptosis.…”

Section: Introductionmentioning

confidence: 99%

Quantitative wave function analysis for excited states of transition metal complexes

Mai

Dorn

Fumanal

et al. 2018

Coordination Chemistry Reviews

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134

163

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The character of an electronically excited state is one of the most important descriptors employed to discuss the photophysics and photochemistry of transition metal complexes. In transition metal complexes, the interaction between the metal and the di erent ligands gives rise to a rich variety of excited states, including metal-centered, intra-ligand, metal-to-ligand charge transfer, ligand-to-metal charge transfer, and ligand-to-ligand charge transfer states. Most often, these excited states are identi ed by considering the most important wave function excitation coe cients and inspecting visually the involved orbitals. This procedure is tedious, subjective, and imprecise. Instead, automatic and quantitative techniques for excited-state characterization are desirable. In this contribution we review the concept of charge transfer numbers-as implemented in the TheoDORE package-and show its wide applicability to characterize the excited states of transition metal complexes. Charge transfer numbers are a formal way to analyze an excited state in terms of electron transitions between groups of atoms based only on the well-de ned transition density matrix. Its advantages are many: it can be fully automatized for many excited states, is objective and reproducible, and provides quantitative data useful for the discussion of trends or patterns. We also introduce a formalism for spin-orbit-mixed states and a method for statistical analysis of charge transfer numbers. The potential of this technique is demonstrated for a number of prototypical transition metal complexes containing Ir, Ru, and Re. Topics discussed include orbital delocalization between metal and carbonyl ligands, nonradiative decay through metal-centered states, e ect of spin-orbit couplings on state character, and comparison among results obtained from di erent electronic structure methods.

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“…Several reviewsconcerning the ability of these methodologies together with several applicationsh ave been published in the last years. [32][33][34][35][36][37][38] In the present review,t he differentc omponents needed for ap roperd escription of the dynamics of excited states are described and the pertinent theoretical approaches discussed. A first crucial factor is the computation of the energy differences between the various spin states involved in the process.…”

Section: Introductionmentioning

confidence: 99%

Deactivation of Excited States in Transition‐Metal Complexes: Insight from Computational Chemistry

Sousa

Alías-Rodríguez

Domingo

et al. 2018

Chemistry A European J

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Investigation of the excited-state decay dynamics of transition-metal systems is a crucial step for the development of photoswitchable molecular based materials with applications in growing fields as energy conversion, data storage, or molecular devices. The photophysics of these systems is an entangled problem arising from the interplay of electronic and geometrical rearrangements that take place on a short time scale. Several factors play a role in the process: various electronic states of different spin and chemical character are involved, the system undergoes important structural variations and several nonradiative processes can occur. Computational chemistry is a useful tool to get insight into the microscopic description of the photophysics of these materials, since it provides unique information about the character of the electronic spin states involved, the energetics and time evolution of the system. In this review article, we present an overview of the state of the art methodologies available to address the several aspects that have to be incorporated to properly describe the deactivation of excited states in transition-metal complexes. The most recent developments in theoretical methods are discussed and illustrated with examples.

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Using computational chemistry to design Ru photosensitizers with directional charge transfer

Cited by 63 publications

References 222 publications

Theoretical Investigation of the Electron‐Transfer Dynamics and Photodegradation Pathways in a Hydrogen‐Evolving Ruthenium–Palladium Photocatalyst

Theoretical Investigation of the Electron‐Transfer Dynamics and Photodegradation Pathways in a Hydrogen‐Evolving Ruthenium–Palladium Photocatalyst

Quantitative wave function analysis for excited states of transition metal complexes

Deactivation of Excited States in Transition‐Metal Complexes: Insight from Computational Chemistry

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