The Green Box: An Electronically Versatile Perylene Diimide Macrocyclic Host for Fullerenes
authors Barendt, TA; Myers, WK; Cornes, SP; Lebedeva, MA; Porfyrakis, K; Marques, I; Felix, V; Beer, PD
nationality International
journal JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
keywords CHARGE-TRANSFER; ENDOHEDRAL METALLOFULLERENE; SUPRAMOLECULAR CHEMISTRY; PHOTOSYNTHETIC ANTENNA; REORGANIZATION ENERGY; TRIPLET ENERGY; C-60 FULLERENE; ACCEPTOR DYAD; DONOR; ANION
abstract The powerful electron accepting ability of fullerenes akes them ubiquitous components in biomimetic donor-acceptor systems that model the intermolecular electron transfer processes of Nature's photosynthetic center. Exploiting perylene diimides (PDIs)The powerful electron accepting ability of fullerenes makes them ubiquitous components in biomimetic donor-acceptor systems that model the intermolecular electron transfer processes of Nature's photosynthetic center. Exploiting perylene diimides (PDIs) as components in cyclic host systems for the noncovalent recognition of fullerenes is unprecedented, in part because archetypal PDIs are also electron deficient, making dyad assembly formation electronically unfavorable. To address this, we report the strategic design and synthesis of a novel large, macrocyclic receptor composed of two covalently strapped electron-rich bis-pyrrolidine PDI panels, nicknamed the Green Box due to its color. Through the principle of electronic complementarity, the Green Box exhibits strong recognition of pristine fullerenes (C-60/70), with the noncovalent ground and excited state interactions that occur upon fullerene guest encapsulation characterized by a range of techniques including electronic absorption, fluorescence emission, NMR and time-resolved EPR spectroscopies, cyclic voltammetry, mass spectrometry, and DFT calculations. While relatively low polarity solvents result in partial charge transfer in the host donor-guest acceptor complex, increasing the polarity of the solvent medium facilitates rare, thermally allowed full electron transfer from the Green Box to fullerene in the ground state. The ensuing charge separated radical ion paired complex is spectroscopically characterized, with thermodynamic reversibility and kinetic stability also demonstrated. Importantly, the Green Box represents a seminal type of C-60/70 host where electron-rich PDI motifs are utilized as recognition motifs for fullerenes, facilitating novel intermolecular, solvent tunable ground state electronic communication with these guests. The ability to switch between extremes of the charge transfer energy continuum is without precedent in synthetic fullerene-based dyads.
publisher AMER CHEMICAL SOC
issn 0002-7863
isbn 1520-5126
year published 2020
volume 142
issue 01-Jan
beginning page 349
ending page 364
digital object identifier (doi) 10.1021/jacs.9b10929
web of science category Chemistry, Multidisciplinary
subject category Chemistry
unique article identifier WOS:000507144400046
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journal analysis (jcr 2019):
journal impact factor 14.612
5 year journal impact factor 14.549
category normalized journal impact factor percentile 92.938
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