The quest for determining one-electron redox potentials of azulene-1-carbonitriles by calculation

Ree, Nicolai; Andersen, Cecilie Lindholm; Kilde, Martin Drøhse; Hammerich, Ole; Nielsen, Mogens Brøndsted; Mikkelsen, Kurt V.

doi:10.1039/c7cp08687c

Cited by 15 publications

(14 citation statements)

References 68 publications

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“…Using M06 and M06-2X, we computed E Fc/Fc + to be 4.97 and 5.31 V, respectively. The former, as expected, shows a better agreement with reported theoretical estimation (4.8 ± 0.1 V) while the latter displays severe overestimation. All redox potentials were evaluated with E DFT = −Δ G / nF , where Δ G stands for taking the A/A + redox couple as example, the change of free energy for A + (soln) + Fc (soln) → A (soln) + Fc + (soln) .…”

Section: Methodssupporting

confidence: 88%

Electronic Structure of Superoxidized Radical Cationic Dodecaborate-Based Clusters

Zhang

Stauber

et al. 2021

J. Phys. Chem. A

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The expanding field of boron clusters has attracted continuous theoretical efforts to understand their diverse structures and unique bonding. We recently discovered a new reversible redox event of B 12 (O-3-methylbutyl) 12 in which the superoxidized radical cationic form [B 12 (O-3-methylbutyl) 12 ] •+ was identified and isolated for the first time. Herein, comprehensive (TD-)DFT studies in tandem with electrochemical experiments were employed to demonstrate the generality of the reported behavior across perfunctionalized B 12 (OR) 12 clusters (R = aryl or alkyl). While the spin density of radical cationic clusters is delocalized in the core region, the oxidation brings about notable gains of positive partial charges on the supporting groups whose electronics can readily tune the redox potential of the 0/•+ couple. The underlying changes of frontier orbitals were elucidated, and the resulting [B 12 (OR) 12 ] •+ species manifest a general diagnostic absorption as a consequence of mixed local/chargetransfer excitations.

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Section: Methodssupporting

confidence: 88%

Electronic Structure of Superoxidized Radical Cationic Dodecaborate-Based Clusters

Zhang

Stauber

et al. 2021

J. Phys. Chem. A

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“…Validation of our computational method used for determination of redox potentials was supported by a linear correlation plot (LCP) of experimental ( E exp ) and calculated absolute ( E abs ) redox potentials (Figure 5; Figure ). A nearly perfect correlation between experimental and calculated redox potentials using CAM‐B3LYP/6‐31+g(d,p) is observed, validating the good performance of this method previously observed in the work of Ree et al 35 The LCP of M06‐2X/6‐31+G(d,p) shows much worse correlation, which can be tracked back as a trend to overestimate the oxidation potential; M06‐2X/6‐31+G(d,p) should not be disregarded as a method as its predictions and hence errors are systematic. Omitting diffuse functions (6‐31G(d,p)) significantly deteriorates the correlation observed for the CAM‐B3LYP and the M06‐2X methods (Figure ).…”

Section: Resultssupporting

confidence: 86%

Subphthalocyanine–triangulene dyads: Property tuning for light‐harvesting device applications

Rasmussen

Jespersen

Blacque

et al. 2022

Energy Science & Engineering

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Organic photovoltaics relies on the development of stable chromophores and redox‐active organic molecules with tailor‐made HOMO/LUMO energies. Here, we present the synthesis and properties of novel dyads composed of boron subphthalocyanine (SubPc) and triangulene units, connected either at the peripheral position of the subphthalocyanine or at the axial boron. The connectivity has strong implications for the absorption and fluorescence properties of the dyads, as well as their redox properties. While the SubPc unit has a bowl shape, triangulene is a planar structural unit that allows dyads to dimerize in the solid state on account of π‐stacking interactions as shown by X‐ray crystallography of one of the dyads. The electronic properties were also studied computationally by density functional theory methods. Excellent agreement between experimental and computed data were obtained, showing that our computational method is a strong tool in the rational design of optimum molecules to ultimately obtain finely tuned molecules for device applications.

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“… a Measured in CH 2 Cl 2 (1.0 × 10 –5 M). b Measured in CH 2 Cl 2 (1.0 × 10 –6 M). c Values in 10 4 L mol –1 cm –1 . d Calculated at the B3LYP-D/6-31G(d) level. The t Bu groups were omitted for simpler calculations. e Oscillator strength. f Absolute fluorescence quantum yield. g Half-wave potential obtained from cyclic voltammetry (0.5 mM in CH 2 Cl 2 , 0.1 M n Bu 4 NPF 6 electrolyte, 100 mV/s scan rate). h Calculated from the first oxidation potential and calibrated against the ferrocene–ferrocenium (F c /F c + ) redox couple (−4.8 eV below the vacuum level) …”

Section: Resultsmentioning

confidence: 99%

Dephosphinylative [4 + 2] Benzannulation of Phosphinyl Ynamines: Application to the Modular Synthesis of Polycyclic Aromatic Amines

et al. 2021

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A series of 9-amino-10-halophenanthrenes were synthesized through a one-pot process, including dephosphinylative Sonogashira–Hagihara coupling of 2-bromobiphenyls with air-stable phosphinyl ynamines, followed by halonium-promoted [4 + 2] benzannulation of the resulting 2-(aminoethynyl)biphenyls. Nonsubstituted and methyl-substituted 2-bromobiphenyls rapidly underwent the Sonogashira–Hagihara aminoethynylation and the halogenative Friedel–Crafts benzannulation to provide the corresponding amino(halo)phenanthrenes in high yields, while electron-sufficient and -deficient substrates did slowly undergo the former and the latter to result in low yields, respectively. This protocol worked well for the syntheses of highly π-extended aminophenanthrenes and aminobenzonaphthothiophenes with different optical properties. Further application of this approach between 2,2″- and 2′,5′-dibromo-p-terphenyls with phosphinyl ynamines led to the regioselective formation of 6,13-diamino-5,12-dihalo- and 5,12-diamino-6,13-dihalo-dibenz[a,h]anthracenes via dual aminoethynylation and [4 + 2] benzannulation. The obtained analogues showed different ultraviolet–visible absorption and photoluminescence spectra with different emission quantum yields in CH2Cl2 solution and the powder state.

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The quest for determining one-electron redox potentials of azulene-1-carbonitriles by calculation

Abstract: Accurate predictions of redox potentials through a simple methodology employing methods that are all implemented in standard electronic structure packages.

Cited by 15 publications

References 68 publications

Electronic Structure of Superoxidized Radical Cationic Dodecaborate-Based Clusters

Electronic Structure of Superoxidized Radical Cationic Dodecaborate-Based Clusters

Subphthalocyanine–triangulene dyads: Property tuning for light‐harvesting device applications

Dephosphinylative [4 + 2] Benzannulation of Phosphinyl Ynamines: Application to the Modular Synthesis of Polycyclic Aromatic Amines

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