Through-shell oxidation and reduction reactions of guests in a hollow container single molecule

Robbins, Timothy A.; Cram, Donald J.

doi:10.1021/ja00078a082

Cited by 35 publications

(24 citation statements)

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“…In this regard, Cram and his co-workers have demonstrated that cyclobutadiene is stabilized inside these hosts, [15] proton-transfer equilibria are strongly affected by encapsulation, [16] and encapsulated guests can undergo chemical oxidation or reduction reactions. [17] Very recently, Balzani and co-workers [18,19] as well as Farran et al [20,21] have investigated the photophysical properties of encapsulated guests. Here we report, for the first time, the electrochemical behavior of ferrocene encapsulated inside these intriguing molecular containers.…”

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confidence: 99%

Electrochemistry of Encapsulated Guests: Ferrocene inside Cram's Hemicarcerands

1998

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The voltammetric behavior of ferrocene encapsulated inside two hemicarcerand hosts was investigated in dichloromethane and tetrachloroethane solutions. Molecular encapsulation led to substantial changes in the anodic voltammetric behavior of the ferrocene nucleus. Generally, encapsulated ferrocene exhibited a more positive halfwave oxidation potential and a lower apparent standard rate constant of heterogeneous electron transfer than uncomplexed ferrocene under identical experimental conditions. Whereas the anodic shift of the half-wave potential probably results from the hindered solvation of the positively charged, oxidized ferrocene inside the nonpolar hemicarcerand cavities, the observed decrease in electron transfer rate seems to arise primarily from the increased molecular mass of the electro-inactive species and the longer distance of maximum approach between the ferrocene center and the electrode surface which is imposed by the encapsulating host. Generally, electrochemical oxidation did not significantly alter the slow rate of ferrocene guest dissociation or release from the hemicarceplexes surveyed.

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confidence: 99%

Electrochemistry of Encapsulated Guests: Ferrocene inside Cram's Hemicarcerands

1998

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“…An oxidation -reduction cycle for hydroquinones 16 -19 could be carried out in the interior of 4 (Figure 9.9 ). 24 Oxidation with Ce(NH 4 ) 2 (NO 2 ) 6 -silica gel − CDCl 3 or Tl(O 2 CCF 3 ) 3 − CCl 4 led to the parent incarcerated quinones 20 -23 in essentially quantitative yields.…”

Section: Electron Transfer Reactionsmentioning

confidence: 99%

Reactions Inside Carcerands

Warmuth

2010

Molecular Encapsulation

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“…(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) active intermediates have been generated and stabilized by preventing their dimerization or the reaction with bulkphase reactants that are too large to enter the inner phase. [6][7][8][9][10][11][12][13][14][15][16][17] Encapsulation has also been applied to investigate fundamental aspects of electron and energy transfer processes, [18][19][20][21][22] to change and control the rate and regiochemistry of bimolecular reactions, [23][24][25][26][27][28][29][30][31][32][33] to amplify reactions, [34] and to alter the position of chemical equilibria. [35] Recently, Rebek and co-workers and Fujita and coworkers showed that Diels-Alder reactions and photochemical [2+2] additions are strongly accelerated in the presence of a self-assembled capsule or coordination cage.…”

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confidence: 99%

Inner‐Phase Reaction Dynamics: The Influence of Hemicarcerand Polarizability and Shape on the Potential Energy Surface of an Inner‐Phase Reaction

et al. 2005

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The thermal decomposition of six phenyldiazirine (2) hemicarceplexes and the spectroscopic properties of these hemicarceplexes, as well as those of one spiro[cyclobutabenzene-1(2H),3Ј-diazirine] (1) and one p-tolyldiazirine (3) hemicarceplex, have been investigated in order to determine the effect of a hemicarcerand on the potential energy surface of an inner-phase reaction. These hemicarceplexes have pentyl or phenethyl feet groups, three tetramethylene linkers and differ in the nature of one linker group X as follows: 1: X = (CH 2 ) 5 ; 2: X = (CH 2 ) n (n = 2, 3, 4), (S,S)-CH 2 CH[OC(CH 3 ) O]CHCH 2 and ortho-CH 2 C 6 H 4 CH 2 ; 3: X = (CH 2 ) 4 . The effect of the linker group X on the structure of the phenyldiazirine hemicarceplexes was analyzed by MM2 force field calculations and leads to a change in the bending of the inner phase, which increases in the order (S,S)-CH 2 CH[OC(CH 3 ) O]CHCH 2 Ͼ (CH 2 ) 4 Ͼ (CH 2 ) 3 Ͼ (CH 2 ) 2 Ͼ ortho-CH 2 C 6 H 4 CH 2 and to a shortening of the center-to-center distance between the two cavitands of the host, which decreases in the order (S,S)-CH 2 CH[OC(CH 3 )O]CHCH 2 Ͻ (CH 2 ) 4 Ͻ (CH 2 ) 3 Ͻ (CH 2 ) 2 Ͻ ortho-CH 2 C 6 H 4 CH 2 . All hemicarceplexes show large red shifts of the diazirine n-π*-transition in their UV/Vis absorption spectra. From the red shifts and from plots of the n-π*-excitation energy of the free diazirines against the solvent polarizability P, the inner-phase po-

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Through-shell oxidation and reduction reactions of guests in a hollow container single molecule

Cited by 35 publications

References 0 publications

Electrochemistry of Encapsulated Guests: Ferrocene inside Cram's Hemicarcerands

Electrochemistry of Encapsulated Guests: Ferrocene inside Cram's Hemicarcerands

Reactions Inside Carcerands

Inner‐Phase Reaction Dynamics: The Influence of Hemicarcerand Polarizability and Shape on the Potential Energy Surface of an Inner‐Phase Reaction

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