Photoinduced Charge Shifts and Electron Transfer in Viologen–Tetraphenylborate Complexes: Push–Pull Character of the Exciplex

Santos, Willy G.; Budkina, Darya S.; Deflon, Victor M.; Tarnovsky, Alexander N.; Cardoso, Daniel; Forbes, Malcolm D. E.

doi:10.1021/jacs.7b01946

Cited by 44 publications

(72 citation statements)

References 30 publications

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“…1 Viologens form ion-pair charge transfer (IPCT) complexes with many inorganic and organic anions of electron donor nature. For example, N,N 0 -dimethyl-4,4 0bipyridinium (methyl viologen, MV 2+ ) forms MV 2+ X À ion pairs with anions X À = F À , Cl À , Br À , I À , perchlorate, sulphate 2 and tetraphenylborate, [3][4][5] which have a specific charge transfer band in their absorption spectra. It falls between 350 and 500 nm, depending on the solvent and the counter anion.…”

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confidence: 99%

Strong ion pair charge transfer interaction of 1,8-naphthalimide–bipyridinium conjugates with basic anions – towards the development of a new type of turn-on fluorescent anion sensors

et al. 2019

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confidence: 99%

Strong ion pair charge transfer interaction of 1,8-naphthalimide–bipyridinium conjugates with basic anions – towards the development of a new type of turn-on fluorescent anion sensors

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“…This phenomenon corresponds to negative solvatochromism [41]. More recently, Santos et al reported on the photoinduced charge shifts in some viologen-tetraphenylborate complexes, which were studied by means of steady-state and time-resolved spectroscopic techniques [24]. An interesting reversible on-off photoswitching aptitude was observed in the solid state.…”

Section: Charge Transfer Complexes Of Viologensmentioning

confidence: 98%

“…In all these cases, the reducing species transfer one electron to the electron-deficient viologen skeleton in an inter-or intra-molecular fashion. Light irradiation can trigger charge transfer from the counter anion of a viologen (BPh4) − [24], [Fe II (CN)6] 4− [25], etc. ( Figure 2b) and the photochromism of viologens is attributed to this effect [18].…”

Section: The Strong Electron-withdrawing Character Of Viologensmentioning

confidence: 99%

“…Later on, Monk et al studied in depth the energetics and kinetics of the formation of such complexes [87] and reported useful information on this important type of CTC and very similar spectral results with Nakahara and Wang. recently, Santos et al reported on the photoinduced charge shifts in some viologentetraphenylborate complexes, which were studied by means of steady-state and time-resolved spectroscopic techniques [24]. An interesting reversible on-off photoswitching aptitude was observed in the solid state.…”

Section: Charge Transfer Complexes Of Viologensmentioning

confidence: 99%

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Mono- and Di-Quaternized 4,4′-Bipyridine Derivatives as Key Building Blocks for Medium- and Environment-Responsive Compounds and Materials

Papadakis

2019

Molecules

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Mono-and di-quaternized 4,4 -bipyridine derivatives constitute a family of heterocyclic compounds, which in recent years have been employed in numerous applications. These applications correspond to various disciplines of research and technology. In their majority, two key features of these 4,4 -bipyridine-based derivatives are exploited: their redox activity and their electrochromic aptitude. Contemporary materials and compounds encompassing these skeletons as building blocks are often characterized as multifunctional, as their presence often gives rise to interesting phenomena, e.g., various types of chromism. This research trend is acknowledged, and, in this review article, recent examples of multifunctional chromic materials/compounds of this class are presented. Emphasis is placed on solvent-/medium-and environment-responsive 4,4 -bipyridine derivatives. Two important classes of 4,4 -bipyridine-based products with solvatochromic and/or environment-responsive character are reviewed: viologens (i.e., N,N -disubstituted derivatives) and monoquats (i.e., monosubstituted 4,4 -bipyridine derivatives). The multifunctional nature of these derivatives is analyzed and structure-property relations are discussed in connection to the role of these derivatives in various novel applications.Molecules 2020, 25, 1 2 of 30 recent) underlining the high versatility of this class of compounds [9,10,[12][13][14][15]. Perhaps, the most reviewed subject regarding the viologens is their electrochromism [13,14,16]. Viologens are known to undergo one-electron reductions electrochemically ( Figure 2) yielding colorful radicals i.e., cations that are stable in the absence of O 2 . Yet, their chromism can also be triggered through various stimuli (including light, heat, solvents, presence of various chemical species, pressure, etc.). All these possibilities shape the very versatile "chromic character" of viologens and generally of 4,4 -bipyridine derivatives. Even though this "chromic character" has only recently started gaining more attention and there is an increasing number of research articles emphasizing on the alternative uses of 4,4 -bipyridine derivatives, there are no reviews in this growing area up until now. Such an attempt is presented in this review paper with an emphasis on medium-and environment-responsive compounds and materials based on 4,4 -bipyridine. Primary focus is placed on viologen-involving solvatochromic systems as well as materials and compounds of this class whose chromic behavior is dependent on various environment stimuli. Molecules 2018, 23, x 2 of 30 Figure 2. Schemes depicting (a) the electrochromic cycle (1) and (b) the photochromic cycle of paraquat (A, counter anion). Structure and Properties of Viologens The Strong Electron-Withdrawing Character of ViologensThe strong electron-withdrawing character of viologens has been widely exploited in numerous molecular architectures and materials. Viologens can undergo reversible one-electron reductions forming radical cations (Figure 2a), which are vividly colo...

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“…The chromic behaviour of viologen-based polymers has been mainly related to a variety of structural factors, such as the electron-donating ability of the donor, the electronaccepting ability of the acceptor, the packing arrangement, the intermolecular interactions, and the orientation, position and especially the distance between the electron donor and acceptor (Sun et al, 2018;Santos et al, 2017), which may be easily studied in detail for the most versatile chromic materials. However, in this field, determining the decisive impact on photochromism of viologen-based compounds is still an obstacle, because there is more than one possible factor, e.g.…”

Section: Introductionmentioning

confidence: 99%

The photochromic behaviour of two viologen salts modulated by the distances between the halide anions and the cationic N atoms of viologen

Yan

et al. 2019

Acta Crystallogr C

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In recent years, viologens and their derivatives have received much attention due to their various potential applications, ranging from electro-or photochromic devices to clean energy. Generally, viologen compounds exhibit a colour change upon being subjected to an external stimulus. However, the chromic mechanism is still ambiguous, because there are many electron-transfer pathways for a chromic compound that need to be considered. Thus, exploring new chromic viologen-based compounds with one pathway should be important and meaningful. In this article, two new viologen-based derivatives, namely 1-(2cyanobenzyl)-4,4 0 -bipyridinium chloride (o-CBbpyÁCl), C 18 H 14 N 3 + ÁCl À (1), and 1-(2-cyanobenzyl)-4,4 0 -bipyridinium bromide (o-CBbpyÁBr), C 18 H 14 N 3 + ÁBr À (2), have been synthesized and characterized. Interestingly, both isomorphic compounds possess only one electron-transfer pathway, in which 1-(2-cyanobenzyl)-4,4 0 -bipyridinium cations (o-CBbpy) and halide anions are employed as electron donors and acceptors, respectively. Salts 1 and 2 consist of o-CBbpy cations involved ininteractions and hydrogen-bond interactions, and halide anions weakly hydrogen bonded to the viologen cations. The salts show different photoresponsive characteristics under identical conditions, which should be mainly related to the distances between the halide cations and the cationic N atoms of o-CBbpy but not the electronegativities of the halogen atoms. These results should not only help in understanding that the distance of the electron-transfer pathway plays an important role in viologen-based photochromism, but should also guide the design and synthesis of additional photochromic materials.

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Photoinduced Charge Shifts and Electron Transfer in Viologen–Tetraphenylborate Complexes: Push–Pull Character of the Exciplex

Cited by 44 publications

References 30 publications

Strong ion pair charge transfer interaction of 1,8-naphthalimide–bipyridinium conjugates with basic anions – towards the development of a new type of turn-on fluorescent anion sensors

Strong ion pair charge transfer interaction of 1,8-naphthalimide–bipyridinium conjugates with basic anions – towards the development of a new type of turn-on fluorescent anion sensors

Mono- and Di-Quaternized 4,4′-Bipyridine Derivatives as Key Building Blocks for Medium- and Environment-Responsive Compounds and Materials

The photochromic behaviour of two viologen salts modulated by the distances between the halide anions and the cationic N atoms of viologen

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