Why Are Dithienylethene‐Linked Biscobaltocenes so Hard to Photoswitch?

Escribano, Alejandra; Steenbock, Torben; Stork, Conrad; Herrmann, Carmen; Heck, Jürgen

doi:10.1002/cphc.201601146

Cited by 6 publications

(9 citation statements)

References 58 publications

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“…The dotted lines indicate one or two methylene units, resulting in five-membered or six-membered central rings. Both were tested and showed very similar switching properties. , Parts of this figure are reprinted with permission from ref . Copyright 2017 Wiley VCH.…”

Section: Control Of Communication (And Its Transferability)mentioning

confidence: 99%

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Electronic Communication as a Transferable Property of Molecular Bridges?

Herrmann

2019

J. Phys. Chem. A

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Electronic communication through molecular bridges is important for different types of experiments, such as single-molecule conductance, electron transfer, superexchange spin coupling, and intramolecular singlet fission. In many instances, the chemical structure of the bridge determines how the two parts it is connecting communicate, and does so in ways that are transferable between these different manifestations (for example, high conductance often correlates with strong antiferromagnetic spin coupling, and low conductance due to destructive quantum interference correlates with ferromagnetic coupling). Defining electronic communication as a transferable property of the bridge can help transfer knowledge between these different areas of research. Examples and limits of such transferability are discussed here, along with some possible directions for future research, such as employing spin-coupled and mixed-valence systems as structurally wellcontrolled proxies for understanding molecular conductance and for validating first-principles theoretical methodologies, building conceptual understanding for the growing experimental work on intramolecular singlet fission, and developing measures for the transferability of electronic communication as a bridge property.

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Section: Control Of Communication (And Its Transferability)mentioning

confidence: 99%

“…Both were tested and showed very similar switching properties. 228,230 aromatic, Huckel antiaromatic, and Mobius aromatic character, 235 whose transferability between the different forms of electronic communication would be very interesting to study. 3.4.…”

Section: Control Of Communication (And Itsmentioning

confidence: 99%

Electronic Communication as a Transferable Property of Molecular Bridges?

Herrmann

2019

J. Phys. Chem. A

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“…The relative importance of these two not only affects NLO properties, but a stabilization of the closed switch resulting from a large admixture of the closed‐shell form can also suppress photochromic ring opening . Due to its poor switching behavior, the closed‐switch form could not be isolated experimentally, and its structure and properties are therefore not known yet . To decide whether further efforts toward obtaining these data and toward optimizing the switching behavior are worthwhile, we aim at a true first‐principles prediction of the diradical character of the closed switch.…”

Section: Introductionmentioning

confidence: 99%

Structural diradical character

Voigt¹,

Steenbock²,

Herrmann³

2018

J Comput Chem

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A reliable first-principles description of singlet diradical character is essential for predicting nonlinear optical and magnetic properties of molecules. As diradical and closed-shell electronic structures differ in their distribution of single, double, triple, and aromatic bonds, modeling electronic diradical character requires accurate bond-length patterns, in addition to accurate absolute bond lengths. We therefore introduce structural diradical character, which we suggest as an additional measure for comparing first-principles calculations with experimental data. We employ this measure to identify suitable exchangecorrelation functionals for predicting the bond length patterns and electronic diradical character of a biscobaltocene with the potential for photoswitchable nonlinear optical activity. Out of four popular approximate exchange-correlation functionals with different exact-exchange admixtures (BP86, TPSS, B3LYP, TPSSh), the two hybrid functionals TPSSh and B3LYP perform best for diradical bond length patterns, with TPSSh being best for the organometallic validation systems and B3LYP for the organic ones (for which the D3 dispersion correction was included). Still, none of the functionals is suitable for correctly describing relative bond lengths across the range of molecules studied, so that none can be recommended for predictive studies of (potential) diradicals without reservation.

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“…The relative importance of these two not only affects NLO properties, but a stabilization of the closed switch resulting from a large admixture of the closed-shell form can also suppress photochromic ring opening 35,36 . Due to its poor switching behavior, the closed-switch form could not be isolated experimentally, and its structure and properties are therefore not known yet 37 . To decide whether further efforts towards obtaining these data and towards optimizing the switching behavior are worthwhile, we aim at a true first-principles prediction of the diradical character of the closed switch.…”

Section: Introductionmentioning

confidence: 99%

Structural diradical character

Voigt¹,

Steenbock²,

Herrmann³

2018

Preprint

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A reliable first-principles description of singlet diradical character is essential for predicting nonlinear optical and magnetic properties of molecules. Since diradical and closed-shell electronic structures differ in their distribution of single, double, triple and aromatic bonds, modeling electronic diradical character requires accurate bond-length patterns, in addition to accurate absolute bond lengths. We therefore introduce structural diradical character, which we suggest as an additional measure for comparing first-principles calculations with experimental data. We employ this measure to identify suitable exchange-correlation functionals for predicting the bond length patterns and electronic diradical character of a biscobaltocene with the potential for photoswitchable nonlinear optical activity. Out of four popular approximate exchange-correlation functionals with different exact-exchange admixtures (BP86, TPSS, B3LYP, TPSSh), the two hybrid functionals TPSSh and B3LYP perform best for diradical bond length patterns, with TPSSh being best for the organometallic validation systems and B3LYP for the organic ones. Still, none of the functionals is suitable for correctly describing relative bond lengths across the range of molecules studied, so that none can be recommended for predictive studies of (potential) diradicals without reservation.

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Why Are Dithienylethene‐Linked Biscobaltocenes so Hard to Photoswitch?

Cited by 6 publications

References 58 publications

Electronic Communication as a Transferable Property of Molecular Bridges?

Electronic Communication as a Transferable Property of Molecular Bridges?

Structural diradical character

Structural diradical character

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