Quinone‐Based, Redox‐Active Resorcin[4]arene Cavitands

Pochorovski, Igor; Boudon, Corinne; Gisselbrecht, Jean‐Paul; Ebert, Marc‐Olivier; Schweizer, W. Bernd; Diederich, François

doi:10.1002/anie.201106031

Cited by 57 publications

(103 citation statements)

References 28 publications

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“…While electron-poor quinones can act as electron acceptors, in case of our quinone moieties the acceptor property is diminished due to electron-donation from the O-atoms of the cavitand backbone; the first redox potential of the quinone moiety was recorded at −1.1 V. 8 In addition, owing to the stiffness of the linker, direct contact between the quinone walls and the dyes through space is essentially impossible, and electron transfer through the linker arm is very unlikely. Electron transfer from the quinone moieties to the excited dyes would also be accompanied by broad, red-shifted charge-transfer bands in the fluorescence spectra of the cavitands.…”

Section: Discussion On Potential Electron Transfermentioning

confidence: 87%

Experimental and Computational Study of BODIPY Dye-Labeled Cavitand Dynamics

et al. 2014

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Understanding the distance distribution and dynamics between moieties attached to the walls of a resorcin [4]arene cavitand, which is switchable between an expanded kite and a contracted vase form, might enable the use of this molecular system for the study of fundamental distance-dependent interactions. Toward this goal, a combined experimental and molecular dynamics (MD) simulation study on donor/acceptor borondipyrromethene (BODIPY) dyelabeled cavitands present in the vase and kite forms was performed. Direct comparison between anisotropy decays calculated from MD simulations with experimental fluorescence anisotropy data showed excellent agreement, indicating that the simulations provide an accurate representation of the dynamics of the system. Distance distributions between the BODIPY dyes were established by comparing time-resolved Forster resonance energy transfer experiments and MD simulations. Fluorescence intensity decay curves emulated on the basis of the MD trajectories showed good agreement with the experimental data, suggesting that the simulations present an accurate picture of the distance distributions and dynamics in this molecular system and provide an important tool for understanding the behavior of extended molecular systems and designing future applications.

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Section: Discussion On Potential Electron Transfermentioning

confidence: 87%

Experimental and Computational Study of BODIPY Dye-Labeled Cavitand Dynamics

et al. 2014

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“…In order to identify the kite and vase conformations in the Q state by UV/Vis spectroscopy, we utilized the solvent and temperature influence on the vase-kite equilibrium. The stabilization of the kite conformation was shown to be dominant in chlorinated solvents, such as CH 2 Cl 2 and CHCl 3 , whereas the vase conformation is stabilized in polar or aromatic solvents, such as tetrahydrofuran (THF) or benzene at ambient temperatures, which was confirmed by NMR spectroscopy 24,26,31. Lower temperatures are known to favor the kite conformation, while elevated temperatures shift the equilibrium towards the vase form 24,28.…”

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confidence: 87%

“…31 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 18 19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36 37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54 55 56 57 58 59 60 12 spectroscopy of quinoxaline model 4, which corresponds to a single quinoxaline cavitand wall.…”

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confidence: 99%

Paramagnetic Molecular Grippers: The Elements of Six-State Redox Switches

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Pochorovski

et al. 2016

J. Phys. Chem. Lett.

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The development of semiquinone-based resorcin[4]arene cavitands expands the toolbox of switchable molecular grippers by introducing the first paramagnetic representatives. The semiquinone (SQ) states were generated electrochemically, chemically, and photochemically. We analyzed their electronic, conformational, and binding properties by cyclic voltammetry, ultraviolet/visible (UV/vis) spectroelectrochemistry, electron paramagnetic resonance (EPR) and transient absorption spectroscopy, in conjunction with density functional theory (DFT) calculations. The utility of UV/vis spectroelectrochemistry and EPR spectroscopy in evaluating the conformational features of resorcin[4]arene cavitands is demonstrated. Guest binding properties were found to be enhanced in the SQ state as compared to the quinone (Q) or the hydroquinone (HQ) states of the cavitands. Thus, these paramagnetic SQ intermediates open the way to six-state redox switches provided by two conformations (open and closed) in three redox states (Q, SQ, and HQ) possessing distinct binding ability. The switchable magnetic properties of these molecular grippers and their responsiveness to electrical stimuli has the potential for development of efficient molecular devices.

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“…The material science field has reached new dimensions with the study and development of molecules whose structures exhibit uncommon properties such as color change via solvatochromic tautomerism (Yamashita and Abe, 2014), pronounced redox activity in substrates with diverse conformational balances (Pochorovski et al, 2012) (Fig. 51), or an extended biradical behavior (Sun et al, 2014).…”

Section: Natural Products and Total Synthesesmentioning

confidence: 99%

Quinoid systems in chemistry and pharmacology

et al. 2015

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In this paper, we present a brief review of quinoid systems, focusing on their chemical synthesis over the last decade. We address not only major methods of synthesizing quinoids, but also their involvement in biological processes. We highlight their medical relevance and versatility, including antitumor, antiretroviral, or antihypertensive agents, properties determined by their various patterns of substitution. Graphical AbstractKeywords Quinone Á Synthesis Á Cytotoxicity Á Natural products Á Pharmacology Á Redox Abbreviations 3a-HSD 3a-Hydroxysteroid dehydrogenase AIDS Acquired Immune Deficiency Syndrome AlnA Alnumycin A AlnB Alnumycin B BAQ Benzanthracene quinone (7,12-benzo[a] anthraquinone) BPQ Benzo[a]pyrene-7,8-dione CAN Ceric ammonium nitrate CC 50 50 % Cytotoxic concentration CDC25 Cell division cycle phosphatases Cyt Ferricytochrome d-A 2 0 -Deoxyadenosine DBU 1,8-Diazabicyclo[5.4.0]undec-7-ene DDQ 2,3-Dichloro-5,6-dicyano-1,4-benzoquinone d-G, d-Guo 2'-Deoxyguanosine DMF N,N-dimethylformamide DMP Dess-Martin periodinane DMSO

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Quinone‐Based, Redox‐Active Resorcin[4]arene Cavitands

Cited by 57 publications

References 28 publications

Experimental and Computational Study of BODIPY Dye-Labeled Cavitand Dynamics

Experimental and Computational Study of BODIPY Dye-Labeled Cavitand Dynamics

Paramagnetic Molecular Grippers: The Elements of Six-State Redox Switches

Quinoid systems in chemistry and pharmacology

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