Electrically-Driven Chiroptical Switches Based on Axially Dissymmetric 1,1‘-Binaphthyl and Electrochromic Viologens:  Synthesis and Optical Properties

Jiang, Dun; Song, Naiheng; Zhou, Qifeng; Su, Zhixing

doi:10.1021/ol701822u

Cited by 41 publications

(26 citation statements)

References 25 publications

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“…[15] UV/Vis absorption spectra were recorded with a Varian Cary 1E spectrometer. Optical rotations were measured at room temperature using a Jasco Model P-1030 polarimeter.…”

Section: Methodsmentioning

confidence: 99%

“…[15] As shown in Figure 2, both compounds change from colourless (l max < 350 nm) to deep blue (l max = 402 and 610 nm) upon electrochemical reduction to violenes. The CD spectrum also changes, due to electrochromism of the viologen groups.…”

mentioning

confidence: 94%

“…Thus, chiroptical switching molecules (R)-1 and (R)-2 (Scheme 1) are designed and synthesized by introducing viologens to the 2,2'-positions of (R)-1,1'-binaphthyls through short aliphatic spacers. [15] The differences between the two chiral molecules are that (R)-2 has a closed-ring structure, in which the two viologens are locked in proximity, while (R)-1 possesses an open-ring structure, where the two viologen groups have much flexibility in assuming a conformation of lower energy.…”

mentioning

confidence: 99%

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Towards Near‐Infrared Chiroptically Switching Materials: Theoretical and Experimental Studies on Viologen‐Containing 1,1′‐Binaphthyls

et al. 2008

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Chiral materials with large and tunable chiroptical properties (e.g. circular birefringence and circular dichroism) can in principle be used for polarization control in many photonic applications such as imaging, optical communication and information storage. To this end, various chiroptical switching systems that respond to external stimuli such as light, heat, electric fields, and chemicals (e.g. acid-base pH changes) have been developed recently. [1][2][3][4] However, up to now, most studies of chiral materials have focused on chiroptical properties in the UV/Vis spectral region (200-700 nm). To the best of our knowledge, materials exhibiting large chiroptical switching properties in the technologically important near-infrared (NIR) region (700-2000 nm) are not yet known. In line with our efforts in searching highly efficient polarization photonics materials, we have recently established an unambiguous structural model correlating the geometric structure of a chiral molecule with the magnitude of chiroptical properties. Based on this model, novel redox-based molecular chiroptical switches are designed and prepared and these show, to the best of our knowledge, the first significant chiroptical switching in the NIR spectral region. Herein, we report the results of the theoretical modelling and the chiroptical switching properties of the resulting chiral molecules.In order to achieve highly efficient chiroptical switching in the NIR spectral region, pronounced NIR chiroptical properties and an efficient switching mechanism are desired. Although current knowledge in synthesizing NIR chiroptically active materials is limited, it is known from Kirkwood's coupled oscillator model [5,6] and the Rosenfeld equation [6] that when low bandgap or NIR-absorbing chromophores are introduced into an appropriate chiral environment, strong NIR chiroptical properties can be expected. Electrochromism as a switching mechanism appears promising due to its readiness in operation and its ability to yield large and reversible spectroscopic changes in the NIR spectral region.[7] Herein, electrochromic viologens (1,1'-disubstituted 4,4'-bipyridinium salts) are chosen as the chromophores because of their low-energy absorbing properties (e.g. l onset % 800 nm) in the single-electron-reduced radical cation (or violene) state as well as their well-documented electrochromism. [8][9][10] Theoretical modelling is done to illustrate the dependence of chiroptical properties on geometric structures and to aid the rational design of molecular chiroptical switches based on viologens that exhibit pronounced chiroptical properties.Figure 1 a defines the geometric factors affecting chiroptical properties, where m 0i and m 0j represent the transition dipole moments of two asymmetrically positioned viologens, which are nearly collinear along the long axes of the viologens, as calculated by time-dependent density functional linear response theory (TD-DFT) [11] . According to exciton coupled theory, [12, 13] chiroptical properties, such as the expression...

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“…[15] UV/Vis absorption spectra were recorded with a Varian Cary 1E spectrometer. Optical rotations were measured at room temperature using a Jasco Model P-1030 polarimeter.…”

Section: Methodsmentioning

confidence: 99%

mentioning

confidence: 94%

mentioning

confidence: 99%

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Towards Near‐Infrared Chiroptically Switching Materials: Theoretical and Experimental Studies on Viologen‐Containing 1,1′‐Binaphthyls

et al. 2008

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“…Balzani, Williams, Stoddart, and coworkers have reported an elegant three-pole supramolecular switch by making use of this property of TTF. 19 This supramolecular switch is based on a three-component system consisting of tetracationic cyclophane cyclobis (paraquatp-phenylene) (CBPQT 4 þ ) as electron accepting host, macrocyclic polyether 1,5-dinaphtho- [38]crown-10 (1/5DN38C10) as electron donating host and TTF. As expected, neutral TTF (TTF 0 ) can form a 1 : 1 inclusion complexes with CBPQT 4 þ that can be dissociated/reassociated reversibly by cyclic oxidation/ reduction of TTF.…”

Section: Tetrathiafulvalene-based Molecular Switchesmentioning

confidence: 99%

“…The chiral binaphthalene 26 fused with two MV 2 þ units has been studied experimentally and theoretically for creating a new chiroptical switch. 38,39 The CD signal intensities at 410 and 660 nm can be reversibly modulated by redox reaction of the MV 2 þ moiety. Also, the optical rotation can be switched in the wavelength range of 1000-2000 nm upon redox cycles between its violene and tetracationic states.…”

Section: Viologen-based Molecular Switchesmentioning

confidence: 99%

Electroactive Molecules and Supramolecules for Information Processing and Storage

Zhang

Zhu

2009

Electrochemistry of Functional Supramolecular Systems

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Redox‐Controlled Intramolecular Motions Triggered by π‐Dimerization and Pimerization Processes

Kahlfuss¹,

Saint‐Aman²,

Bucher³

2015

Organic Redox Systems

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Electrically-Driven Chiroptical Switches Based on Axially Dissymmetric 1,1‘-Binaphthyl and Electrochromic Viologens: Synthesis and Optical Properties

Cited by 41 publications

References 25 publications

Towards Near‐Infrared Chiroptically Switching Materials: Theoretical and Experimental Studies on Viologen‐Containing 1,1′‐Binaphthyls

Towards Near‐Infrared Chiroptically Switching Materials: Theoretical and Experimental Studies on Viologen‐Containing 1,1′‐Binaphthyls

Electroactive Molecules and Supramolecules for Information Processing and Storage

Redox‐Controlled Intramolecular Motions Triggered by π‐Dimerization and Pimerization Processes

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