Difluorodiazirine (CF2N2): A comparative quantum mechanical study of the first triplet and first singlet excited states

Terrabuio, Luiz Alberto; Haiduke, Roberto Luiz Andrade; Matta, Chérif F.

doi:10.1016/j.cplett.2016.05.032

Cited by 8 publications

(11 citation statements)

References 39 publications

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“…There are also quite a few studies of the 0-0 energies of various states for this derivative, both experimentally [85][86][87] and theoretically. 84,88,89 Formylfluoride. For this formal intermediate between carbonylfluoride and formaldehyde, we note that the CCSDTQ/6-31+G(d) values are bracketed by their CC3 and CCSDT counterparts.…”

Section: Other Wave Function Calculationsmentioning

confidence: 99%

A Mountaineering Strategy to Excited States: Highly Accurate Energies and Benchmarks for Medium Sized Molecules

Loos

Lipparini

Boggio‐Pasqua

et al. 2020

J. Chem. Theory Comput.

175

270

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Section: Other Wave Function Calculationsmentioning

confidence: 99%

A Mountaineering Strategy to Excited States: Highly Accurate Energies and Benchmarks for Medium Sized Molecules

Loos

Lipparini

Boggio‐Pasqua

et al. 2020

J. Chem. Theory Comput.

175

270

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“…111 Unfortunately, no purification or cross-linking data have yet been reported. Furthermore, significantly less is known about CF 2 phenyl carbenes than their CF 3 counterparts, 112 which may have implications on the protein cross-linking efficiency of the fluorous-tagged and all-in-one diaizirines. Moreover, these additional functionalities may also add steps to already long syntheses.…”

Section: Novel Tpd-derived Photo-cross-linkersmentioning

confidence: 99%

Fishing for Drug Targets: A Focus on Diazirine Photoaffinity Probe Synthesis

2018

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Target identification is a high-priority, albeit challenging, aspect of drug discovery. Diazirine-based photoaffinity probes (PAPs) can facilitate the process by covalently capturing transient molecular interactions. This can help identify target proteins and map the ligand's interactome. Diazirine probes have even been incorporated by cellular machinery into proteins. Embarking on the synthesis of customized PAPs, containing either an aliphatic or trifluoromethyl phenyl diazirine, can be a considerable endeavor, particularly for medicinal chemists and chemical biologists new to the field. This review takes a synthetic focus, aiming to summarize available routes, propose new avenues, and illuminate recent advances in diazirine synthesis. Select examples of diazirine photoaffinity labeling applications have been included throughout to provide instructive definition of the advantages and limitations of the technology while simultaneously highlighting how these reagents can be applied in a practical sense.

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“…The topological analysis of electron density allows for direct comparisons between the ground and excited states and permits the isolation of specific effects that determine the energetic landscape. Several groups have reported the results of quantum chemical topology studies of the photophysical and ‐chemical processes of organic systems, describing the electron density redistribution during excitation as a driving force for excited‐state dynamics …”

Section: Introductionmentioning

confidence: 99%

“…Severalg roups have reported the results of quantumc hemical topology studies of the photophysical and -chemical processes of organic systems, describing the electron density redistributiond uring excitation as ad riving force for excited-state dynamics. [40][41][42][43][44][45]…”

Section: Introductionmentioning

confidence: 99%

Origin of the Photoinduced Geometrical Change of Copper(I) Complexes from the Quantum Chemical Topology View

Gutiérrez‐Arzaluz

Ramírez-Palma

Ramírez‐Palma

et al. 2018

Chemistry A European J

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Copper(I) complexes (CICs) are of great interest due to their applications as redox mediators and molecular switches. CICs present drastic geometrical change in their excited states, which interferes with their luminescence properties. The photophysical process has been extensively studied by several time‐resolved methods to gain an understanding of the dynamics and mechanism of the torsion, which has been explained in terms of a Jahn–Teller effect. Here, we propose an alternative explanation for the photoinduced structural change of CICs, based on electron density redistribution. After photoexcitation of a CIC (S0→S1), a metal‐to‐ligand charge transfer stabilizes the ligand and destabilizes the metal. A subsequent electron transfer, through an intersystem crossing process, followed by an internal conversion (S1→T2→T1), intensifies the energetic differences between the metal and ligand within the complex. The energy profile of each state is the result of the balance between metal and ligand energy changes. The loss of electrons originates an increase in the attractive potential energy within the copper basin, which is not compensated by the associated reduction of the repulsive atomic potential. To counterbalance the atomic destabilization, the valence shell of the copper center is polarized (defined by ∇2ρ(r) and ∇2Vne(r)) during the deactivation path. This polarization increases the magnitude of the intra‐atomic nuclear–electron interactions within the copper atom and provokes the flattening of the structure to obtain the geometry with the maximum interaction between the charge depletions of the metal and the charge concentrations of the ligand.

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Difluorodiazirine (CF2N2): A comparative quantum mechanical study of the first triplet and first singlet excited states

Cited by 8 publications

References 39 publications

A Mountaineering Strategy to Excited States: Highly Accurate Energies and Benchmarks for Medium Sized Molecules

A Mountaineering Strategy to Excited States: Highly Accurate Energies and Benchmarks for Medium Sized Molecules

Fishing for Drug Targets: A Focus on Diazirine Photoaffinity Probe Synthesis

Origin of the Photoinduced Geometrical Change of Copper(I) Complexes from the Quantum Chemical Topology View

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