Configurationally Stable Chiral Dithia‐Bridged Hetero[4]helicene Radical Cation: Electronic Structure and Absolute Configuration

Gliemann, Bettina D.; Petrovic, Ana G.; Zolnhofer, Eva M.; Dral, Pavlo O.; Hampel, Frank; Breitenbruch, Georg; Schulze, Philipp; Raghavan, Vasanthan; Meyer, Karsten; Polavarapu, Prasad L.; Berova, Nina; Kivala, Milan

doi:10.1002/asia.201601452

Cited by 31 publications

(39 citation statements)

References 55 publications

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“…The DF and CID spectral methods have been used to aid in the determination of the ACs of several compounds. 22,[32][33][34][35][36][37][38] In addition, the experimental EDF spectra of binaphthol showed differences due to solvent complexation that followed the trend in solvent polarity. 39 In CDSpecTech, the similarity index SI can be calculated for EA, VA, and Raman spectra, and ESI for ECD, VCD, VROA, EDF, VDF, and VROA spectra, using the parametric function equation 19.…”

Section: Technical Detailsmentioning

confidence: 97%

“…Therefore, during similarity analysis between experimental and predicted VCD spectra, a Sim value of less than~0.4 and ESI value of less than~0.6 cannot unequivocally be used for AC Even though the current illustration (Figures 3, 4, and Tables 2, 3) is limited to VA, VCD, and VDF spectra, the CDSpecTech can do similar analyses for EA, ECD, and EDF and for vibrational Raman, VROA, and CID spectra as well. 22,[31][32][33][34][36][37][38]…”

Section: Similarity Overlap Analysismentioning

confidence: 99%

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CDSpecTech: A single software suite for multiple chiroptical spectroscopic analyses

Covington

Polavarapu

2017

Chirality

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The program CDSpecTech was developed to facilitate the analysis of chiroptical spectra, which include the following: vibrational circular dichroism (VCD) and corresponding vibrational absorption (VA) spectra; vibrational Raman optical activity (VROA) and corresponding vibrational Raman spectra; electronic circular dichroism (ECD) and corresponding electronic absorption (EA) spectra. In addition, the program allows for generating optical rotatory dispersion (ORD) as the Kramers-Kronig transform of ECD spectra. The simulation of theoretical spectra from transition strengths can be achieved using different bandshape profiles. The experimental and simulated theoretical spectra can be visually compared by displaying them together. A unique feature of CDSpecTech is performing spectral analysis using the ratio spectra; i.e., the dimensionless dissymmetry factor (DF) spectrum, which is the ratio of CD to absorption spectra, and the dimensionless circular intensity difference (CID) spectrum, which is the ratio of VROA to vibrational Raman spectra. The quantitative agreement between experimental and simulated theoretical spectra can also be assessed from the numerical similarity overlap between them. Two different similarity overlap methods are available. The program uses a graphical user interface which allows for ease of use and facilitates the analysis. All these features make CDSpecTech a valuable tool for the analysis of chiroptical spectra. The program is freely available on the World Wide Web.

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Section: Technical Detailsmentioning

confidence: 97%

Section: Similarity Overlap Analysismentioning

confidence: 99%

CDSpecTech: A single software suite for multiple chiroptical spectroscopic analyses

Covington

Polavarapu

2017

Chirality

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“…Additionally, we described the utility of a pair of these compounds as red‐ox switches via easy reversible single electron oxidation leading to exceptionally stable radical cations . Indeed, the synthetic methodology we settled out was recently applied for the preparation of a configurational bench stable enantiopure radical cation, and (apparently, vide infra) used for the assembling of DSSCs in which thia‐bridged triarylamines were the donor counterpart. In this update we describe a detailed study on scope and application of the electrophilic sulfur insertion path to TBTH[4]H 3 , with particular emphasis to the regioselective preparation of asymmetric (without a C 2 symmetry axis, i.e.…”

Section: Introductionmentioning

confidence: 99%

Thia‐Bridged Triarylamine Hetero[4]Helicenes: Regioselective Synthesis and Functionalization

et al. 2018

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Thia‐bridged triarylamine hetero[4]helicenes (TBTH[4]H) are a peculiar class of geometrically stable [4]helicenes that have shown promising applications as organic electronic materials. Their structure comprises a bis‐phenothiazine moiety, with a nitrogen atom and an aromatic ring in common, forced into a helix‐shaped arrangement by four carbon–sulfur bonds. We describe a detailed study on the scope and application of the electrophilic sulfur insertion path to TBTH[4]H, with particular emphasis on the regioselective preparation of asymmetric (not dissymmetric) derivatives.

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“…[10] Exploiting the rich chemistry of aromatic amines,b ack in the 1980s, Hellwinkel and Melan [11] reported an elegant molecular design resulting from the exhaustive introductiono fb ridging units at the ortho-position of triphenylamine, which forces the originally propeller-shaped scaffold into av irtually planar geometry (Figure 1b). [12] Various types of bridged triphenylamines have been reported to date, [12,13] including carbonyl, [14] ether, [5,15,16] thioether, [17] dimethylmethylene, [18,19] and diphenylmethylene bridges [20] as well as triphenylamines with two fused pentagons. [21] It has been demonstrated that Hellwinkel's design principle can be adopted to stabilize N-centered radicalcations by delocalization of the radical over the planarized p-system.…”

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confidence: 99%

A Spherically Shielded Triphenylamine and Its Persistent Radical Cation

Schaub

Mekelburg

Dral

et al. 2020

Chemistry A European J

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This work reports the design and synthesis of a sterically protected triphenylamine scaffold which undergoes one‐electron oxidation to form an amine‐centered radical cation of remarkable stability. Several structural adjustments were made to tame the inherent reactivity of the radical cation. First, the parent propeller‐shaped triphenylamine was planarized with sterically demanding bridging units and, second, protecting groups were deployed to block the reactive positions. The efficiently shielded triphenylamine core can be reversibly oxidized at moderate potentials (+0.38 V, vs. Fc/Fc+ in CH2Cl2). Spectroelectrochemistry and chemical oxidation studies were employed to monitor the evolution of characteristic photophysical features. To obtain a better understanding of the impact of one‐electron oxidation on structural and electronic properties, joint experimental and computational studies were conducted, including X‐ray structural analysis, electron paramagnetic resonance (EPR), and density functional theory (DFT) calculations. The sterically shielded radical cation combines various desirable attributes: A characteristic and unobstructed absorption in the visible region, high stability which enables storage for weeks without spectroscopically traceable degradation, and a reliable oxidation/re‐reduction process due to effective screening of the planarized triphenylamine core from its environment.

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Configurationally Stable Chiral Dithia‐Bridged Hetero[4]helicene Radical Cation: Electronic Structure and Absolute Configuration

Cited by 31 publications

References 55 publications

CDSpecTech: A single software suite for multiple chiroptical spectroscopic analyses

CDSpecTech: A single software suite for multiple chiroptical spectroscopic analyses

Thia‐Bridged Triarylamine Hetero[4]Helicenes: Regioselective Synthesis and Functionalization

A Spherically Shielded Triphenylamine and Its Persistent Radical Cation

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