The Quest to Simulate Excited-State Dynamics of Transition Metal Complexes

Zobel, J. Patrick; González, Leticia

doi:10.1021/jacsau.1c00252

Cited by 34 publications

(34 citation statements)

References 281 publications

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“…173−175 At the same time, further developments of precious metal-based complexes (for example, Ru, 167,176,177 Rh, 178,179 Re, 180−182 Ir, 183−185 or Pt 186−188 ) have significantly advanced the field of inorganic photophysics and photochemistry. Regardless of whether complexes of d-, f-, or main group elements are considered, the interplay between synthetic, spectroscopic, and computational work 189 seems crucial for the development of new designer luminophores.…”

Section: Discussionmentioning

confidence: 99%

Luminescent First-Row Transition Metal Complexes

Wegeberg

Wenger

2021

JACS Au

177

234

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Precious and rare elements have traditionally dominated inorganic photophysics and photochemistry, but now we are witnessing a paradigm shift toward cheaper and more abundant metals. Even though emissive complexes based on selected first-row transition metals have long been known, recent conceptual breakthroughs revealed that a much broader range of elements in different oxidation states are useable for this purpose. Coordination compounds of V, Cr, Mn, Fe, Co, Ni, and Cu now show electronically excited states with unexpected reactivity and photoluminescence behavior. Aside from providing a compact survey of the recent conceptual key advances in this dynamic field, our Perspective identifies the main design strategies that enabled the discovery of fundamentally new types of 3d-metal-based luminophores and photosensitizers operating in solution at room temperature.

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Section: Discussionmentioning

confidence: 99%

Luminescent First-Row Transition Metal Complexes

Wegeberg

Wenger

2021

JACS Au

177

234

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“…[58], while simulation of excited state dynamics of coordination compounds has been reviewed very recently in Refs. [64,65].…”

Section: Excited-state Relaxation -Advanced Theoretical Modelsmentioning

confidence: 99%

Ultrafast Spectroscopy of Fe(II) Complexes Designed for Solar‐Energy Conversion: Current Status and Open Questions

et al. 2022

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One major challenge of future sustainable photochemistry is to replace precious and rare transition metals in applications such as energy conversion or electroluminescence by earth‐abundant, cheap, and recyclable materials. This involves using coordination complexes of first row transition metals such as Cu, Cr, or Mn. In the case of iron, which is attractive due to its natural abundance, fundamental limitations imposed by the small ligand field splitting energy have recently been overcome. In this review article, we briefly summarize the present knowledge and understanding of the structure‐property relationships of Fe(II) and Fe(III) complexes with excited state lifetimes in the nanosecond range. However, our main focus is to examine to which extent the ultrafast spectroscopy methods used so far provided insight into the excited state structure and the photo‐induced dynamics of these complexes. Driven by the main question of how to spectroscopically, i. e. in energy and concentration, differentiate the population of ligand‐ vs. metal‐centered states, the hitherto less exploited ultrafast vibrational spectroscopy is suggested to provide valuable complementary insights.

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“…Indeed, each computational model has its own theoretical and/or technical limitations and the number of possible chemical scenarios is so vast that the design of new excited-state methodologies remains a very active field of theoretical quantum chemistry. [10][11][12][13][14][15][16][17][18][19][20][21][22][23] Speaking of difficult tasks, the cyclobutadiene (CBD) molecule has been a real challenge for both experimental and theoretical chemistry for many decades. 24 Due to its antiaromaticity 25 and large angular strain, 26 CBD presents a high reactivity making its synthesis a particularly difficult exercise.…”

Section: Introductionmentioning

confidence: 99%

Reference Energies for Cyclobutadiene: Automerization and Excited States

Monino,

Boggio-Pasqua,

Scemama

et al. 2022

Preprint

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Cyclobutadiene is a well-known playground for theoretical chemists and is particularly suitable to test ground-and excited-state methods. Indeed, due to its high spatial symmetry, especially at the D 4h square geometry but also in the D 2h rectangular arrangement, the ground and excited states of cyclobutadiene exhibit multi-configurational characters and single-reference methods, such as adiabatic time-dependent density-functional theory (TD-DFT) or equation-of-motion coupled cluster (EOM-CC), are notoriously known to struggle in such situations. In this work, using a large panel of methods and basis sets, we provide an extensive computational study of the automerization barrier (defined as the difference between the square and rectangular ground-state energies) and the vertical excitation energies at D 2h and D 4h equilibrium structures. In particular, selected configuration interaction (SCI), multi-reference perturbation theory (CASSCF, CASPT2, and NEVPT2), and coupled-cluster (CCSD, CC3, CCSDT, CC4, and CCSDTQ) calculations are performed. The spin-flip formalism, which is known to provide a qualitatively correct description of these diradical states, is also tested within TD-DFT (combined with numerous exchange-correlation functionals) and the algebraic diagrammatic construction [ADC(2)-s, ADC(2)-x, and ADC(3)] schemes. A theoretical best estimate is defined for the automerization barrier and for each vertical transition energy.

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The Quest to Simulate Excited-State Dynamics of Transition Metal Complexes

Cited by 34 publications

References 281 publications

Luminescent First-Row Transition Metal Complexes

Luminescent First-Row Transition Metal Complexes

Ultrafast Spectroscopy of Fe(II) Complexes Designed for Solar‐Energy Conversion: Current Status and Open Questions

Reference Energies for Cyclobutadiene: Automerization and Excited States

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