PAH/PAH(CF 3 ) n Donor/Acceptor Charge-Transfer Complexes in Solution and in Solid-State Co-Crystals.

Autor: Castro KP; Department of Chemistry, Colorado State University, Fort Collins, CO, 80523, USA., Bukovsky EV; Department of Chemistry, Colorado State University, Fort Collins, CO, 80523, USA., Kuvychko IV; Department of Chemistry, Colorado State University, Fort Collins, CO, 80523, USA., DeWeerd NJ; Department of Chemistry, Colorado State University, Fort Collins, CO, 80523, USA., Chen YS; ChemMatCARS, University of Chicago, Advanced Photon Source, Argonne, IL 60439, USA., Deng SHM; Physical Sciences Division, Pacific Northwest National Laboratory, MS K8 88, P.O. Box 999, Richland, Washington, 99352, USA., Wang XB; Physical Sciences Division, Pacific Northwest National Laboratory, MS K8 88, P.O. Box 999, Richland, Washington, 99352, USA., Popov AA; Leibniz Institute for Solid State and Materials Research, Dresden, 01069, Germany., Strauss SH; Department of Chemistry, Colorado State University, Fort Collins, CO, 80523, USA., Boltalina OV; Department of Chemistry, Colorado State University, Fort Collins, CO, 80523, USA.
Jazyk: angličtina
Zdroj: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2019 Oct 22; Vol. 25 (59), pp. 13547-13565. Date of Electronic Publication: 2019 Oct 07.
DOI: 10.1002/chem.201902712
Abstrakt: A solution, solid-state, and computational study is reported of polycyclic aromatic hydrocarbon PAH/PAH(CF 3 ) n donor/acceptor (D/A) charge-transfer complexes that involve six PAH(CF 3 ) n acceptors with known gas-phase electron affinities that range from 2.11(2) to 2.805(15) eV and four PAH donors, including seven CT co-crystal X-ray structures that exhibit hexagonal arrays of mixed π-stacks with 1/1, 1/2, or 2/1 D/A stoichiometries (PAH=anthracene, azulene, coronene, perylene, pyrene, triphenylene; n=5, 6). These are the first D/A CT complexes with PAH(CF 3 ) n acceptors to be studied in detail. The nine D/A combinations were chosen to allow several structural and electronic comparisons to be made, providing new insights about controlling D/A interactions and the structures of CT co-crystals. The comparisons include, among others, CT complexes of the same PAH(CF 3 ) n acceptor with four PAH donors and CT complexes of the same donor with four PAH(CF 3 ) n acceptors. All nine CT complexes exhibit charge-transfer bands in solution with λ max between 467 and 600 nm. A plot of E(λ max ) versus [IE(donor)-EA(acceptor)] for the nine CT complexes studied is linear with a slope of 0.72±0.03 eV eV -1 . This plot is the first of its kind for CT complexes with structurally related donors and acceptors for which precise experimental gas-phase IEs and EAs are known. It demonstrates that conclusions based on the common assumption that the slope of a CT E(λ max ) versus [IE-EA] plot is unity may be incorrect in at least some cases and should be reconsidered.
(© 2019 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)
Databáze: MEDLINE
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