π‐Electron Redox Systems of Heavier Group 15 Elements

Sasamori, Takahiro; Tokitoh, Norihiro; Streubel, Rainer

doi:10.1002/9781118858981.ch20

Cited by 5 publications

(4 citation statements)

References 94 publications

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“…To clarify this point, the commutation of the system was investigated by using an oxidizing reagent such as NOSbF 6 (0.87 V vs Fc/Fc + ) 45 which is largely used to evidence mixed valence in electroactive species by UV−visible−NIR spectroscopy 46,47 or generating one-electron oxidation of organic donors. 48 As expected, a drastic change of the UV−visible spectra upon the addition of NOSbF 6 aliquots is observed. At the end, we can notice that this addition of oxidizing reagent leads to an identical spectrum as the one obtained after stimulation with an excess of acid as shown in Figure 7 for compound 1.…”

Section: ■ Results and Discussionsupporting

confidence: 76%

“…To clarify this point, the commutation of the system was investigated by using an oxidizing reagent such as NOSbF 6 (0.87 V vs Fc/Fc + ) which is largely used to evidence mixed valence in electroactive species by UV–visible–NIR spectroscopy , or generating one-electron oxidation of organic donors . As expected, a drastic change of the UV–visible spectra upon the addition of NOSbF 6 aliquots is observed.…”

Section: Resultsmentioning

confidence: 85%

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BT-2-BOX: An Assembly toward Multimodal and Multilevel Molecular System Simple as a Breeze

et al. 2019

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The design of multistate/multifunctional molecular systems arouses a lot of interest. Such compounds are able to commutate between two metastable states by the application of an external stimulation such as light, heat, protons, or electrons. In this context, we are interested in molecular switches based on indolino-oxazolidine (BOX) which is a relatively less-known sub-class of multimodal addressable units. Their particularity consists of the possibility to induce the opening/closing of the oxazolidine ring by using indifferently light, electrochemical, or acido-basic stimulation. Up to now, most of the reported systems based on BOX have allowed to modulate a molecular property but only between two discrete levels which can only be extended by their association with other classical switchable unit such as a dithienylethene unit. For this reason, we report here our effort to enhance the number of metastable states by simply connecting two identical BOX units by a bithiophene (BT) linker. The resulting system's ability to switch between the three possible metastable states was investigated. Irrespective of the nature of the stimulation, full commutation of the system could be reached, but our work mainly revealed that the opening of both oxazolidine rings occurs in a stepwise manner. If this unreported selectivity upon a unique stimulus with two identical switchable units is observed irrespective of the stimulation, it must be pointed out that its efficiency depends on the nature of the latter. The direct stimulation with acid or light leads to the coexistence of the three different states of the system over a broad stimulation period. On the contrary, the indirect stimulation of BOX via an electromediated process due to the electroactivity of BT enhances the selective addressability between both identical BOX units.

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Section: ■ Results and Discussionsupporting

confidence: 76%

Section: Resultsmentioning

confidence: 85%

BT-2-BOX: An Assembly toward Multimodal and Multilevel Molecular System Simple as a Breeze

et al. 2019

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“…This efficient formation of 2+H + under an electrochemical stimulation have been easily confirmed by treating a solution of 2 by an oxidizing reagent and monitoring the reaction by UV‐Visible spectroscopy. Indeed, the uses of NOSbF 6 (0.87 V vs Fc/Fc + ) [27] was largely reported for such purpose to evidence mixed valence in electroactive species [28] or generating one‐electron oxidation of organic donors [29] . As noticed with acid, the addition of NOSbF 6 aliquots to a solution of compound 2 leads to observe a bathochromic shift of the low energy band and an hypo and a bathochromic effect on the band at higher energy assigned to 2+H + (see SI).…”

Section: Resultsmentioning

confidence: 99%

Vinylpyrimidine‐Functionalized Triphenylamines: Bimodal Molecular Switches and Multilevel Systems

2022

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Due to their numerous potential applications, the interest for the elaboration of new molecular switch has never stop to grow. Among them, multi‐modal systems, where the switching between two different metastable states can be induced by using indifferently several kinds of stimulation, have a special place. In this study, we present our efforts to develop a class of multi‐modal systems based on the association of a triphenylamine core with vinylpyrimidine units that exhibits nice acido and electrochromic properties. The most performant ones can present up to three different forms allowing to modulate their absorption and luminescence properties over three discrete levels. In order to provide limitations and outlooks for such systems, their switching behaviors have been rationalized by the help of DFT and TD‐DFT calculations.

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“…, 4,5,6-triphospha[3]radialene, was studied too, which could be reduced to structurally confirmed dianions. Furthermore, cyclic voltammetry studies showed a reversible initial one-electron reduction and, on further scanning, revealed a second reversible redox couple, but no experiments aimed at demonstrating suitability as electrode materials were performed such as multicycle voltammograms, i.e ., the robustness of the cycles was not proven. − …”

Section: Introductionmentioning

confidence: 99%

Reversible Redox Chemistry of Anionic Imidazole-2-thione-Fused 1,4-Dihydro-1,4-diphosphinines

et al. 2022

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Anionic 1,4-dihydro-1,4-diphosphinines were synthesized from tricyclic 1,4-diphosphinines and isolated as blue powdery salts M[ 2a – 2c ]. Reaction of solutions of these monoanions with iodomethane led to P -methylated compounds 3a – 3c . An oxidation/reduction cycle was examined, starting from solutions of K[ 2a ] via P–P coupled product 4a and back to K[ 2a ], and the recyclability and redox chemistry of this cycle were confirmed by experimental and simulated cyclic voltammetry analysis, which is proposed as a potential 2-electron cathode for rechargeable cells. TD-DFT studies were used to examine species that might be involved in the process.

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π‐Electron Redox Systems of Heavier Group 15 Elements

Cited by 5 publications

References 94 publications

BT-2-BOX: An Assembly toward Multimodal and Multilevel Molecular System Simple as a Breeze

BT-2-BOX: An Assembly toward Multimodal and Multilevel Molecular System Simple as a Breeze

Vinylpyrimidine‐Functionalized Triphenylamines: Bimodal Molecular Switches and Multilevel Systems

Reversible Redox Chemistry of Anionic Imidazole-2-thione-Fused 1,4-Dihydro-1,4-diphosphinines

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