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Intramolecular Energy and Electron Transfer Within a Diazaperopyrenium-Based Cyclophane

Gong, Xirui and Young, Ryan M. and Hartlieb, Karel J. and Miller, Claire and Wu, Yilei and Xiao, Hai and Li, Peng and Hafezi, Nema and Zhou, Jiawang and Ma, Lin and Cheng, Tao and Goddard, William A., III and Farha, Omar K. and Hupp, Joseph T. and Wasielewski, Michael R. and Stoddart, J. Fraser (2017) Intramolecular Energy and Electron Transfer Within a Diazaperopyrenium-Based Cyclophane. Journal of the American Chemical Society, 139 (11). pp. 4107-4116. ISSN 0002-7863.

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Molecules capable of performing highly efficient energy transfer and ultrafast photo-induced electron transfer in well-defined multichromophoric structures are indispensable to the development of artificial photosynthetic systems. Herein, we report on the synthesis, characterization and photophysical properties of a rationally designed multichromophoric tetracationic cyclophane, DAPPBox^(4+), containing a diazaperopyrenium (DAPP^(2+)) unit and an extended viologen (ExBIPY^(2+)) unit, which are linked together by two p-xylylene bridges. Both ^1H NMR spectroscopy and single crystal X-ray diffraction analysis confirm the formation of an asymmetric, rigid, box-like cyclophane, DAPPBox^(4+). The solid-state superstructure of this cyclophane reveals a herringbone-type packing motif, leading to two types of π···π interactions: (i) between the ExBIPY^(2+) unit and the DAPP^(2+) unit (π···π distance of 3.7 Å) in the adjacent parallel cyclophane, as well as (ii) between the ExBIPY^(2+) unit (π···π distance of 3.2 Å) and phenylene ring in the closest orthogonal cyclophane. Moreover, the solution-phase photophysical properties of this cyclophane have been investigated by both steady-state and time-resolved absorption and emission spectroscopies. Upon photoexcitation of DAPPBox^(4+) at 330 nm, rapid and quantitative intramolecular energy transfer occurs from the ^1*ExBIPY^(2+) unit to the DAPP^(2+) unit in 0.5 ps to yield ^1*DAPP^(2+). The same excitation wavelength simultaneously populates a higher excited state of ^1*DAPP^(2+) which then undergoes ultrafast intramolecular electron transfer from ^1*DAPP^(2+) to ExBIPY^(2+) to yield the DAPP^(3+•) – ExBIPY^(+•) radical ion pair in τ = 1.5 ps. Selective excitation of DAPP^(2+) at 505 nm populates a lower excited state where electron transfer is kinetically unfavorable.

Item Type:Article
Related URLs:
URLURL TypeDescription Information
Wu, Yilei0000-0001-6756-1855
Xiao, Hai0000-0001-9399-1584
Zhou, Jiawang0000-0002-2399-0030
Cheng, Tao0000-0003-4830-177X
Goddard, William A., III0000-0003-0097-5716
Farha, Omar K.0000-0002-9904-9845
Hupp, Joseph T.0000-0003-3982-9812
Wasielewski, Michael R.0000-0003-2920-5440
Stoddart, J. Fraser0000-0003-3161-3697
Additional Information:© 2017 American Chemical Society. ACS AuthorChoice - This is an open access article published under an ACS AuthorChoice License, which permits copying and redistribution of the article or any adaptations for non-commercial purposes. Received: December 31, 2016; Published: February 22, 2017. This research was conducted as part of the Joint Center of Excellence in Integrated Nanosystems at King Abdulaziz City for Science and Technology (KACST) and Northwestern University (NU). The authors thank both KACST and NU for their continued support of this research. This work was also supported by the Chemical Sciences, Geosciences, and Biosciences Division, Office of Basic Energy Sciences, U.S. Department of Energy (DOE) under grant no. DE-FG02-99ER14999 (M.R.W.). J.T.H. and O.K.F. gratefully acknowledge financial support by the U.S. DOE, Office of Science, Office of Basic Energy Sciences (grant No. DE-FG02 87ER13808) and Northwestern University. H.X. and W.A.G. were supported by NSF (EFRI-00155EI-1332411). The authors declare no competing financial interest.
Funding AgencyGrant Number
King Abdulaziz City for Science and Technology (KACST)UNSPECIFIED
Northwestern UniversityUNSPECIFIED
Department of Energy (DOE)DE-FG02-99ER14999
Department of Energy (DOE)DE-FG02 87ER13808
Issue or Number:11
Record Number:CaltechAUTHORS:20170224-102713340
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Official Citation:Intramolecular Energy and Electron Transfer within a Diazaperopyrenium-Based Cyclophane Xirui Gong, Ryan M. Young, Karel J. Hartlieb, Claire Miller, Yilei Wu, Hai Xiao, Peng Li, Nema Hafezi, Jiawang Zhou, Lin Ma, Tao Cheng, William A. Goddard, III, Omar K. Farha, Joseph T. Hupp, Michael R. Wasielewski, and J. Fraser Stoddart Journal of the American Chemical Society 2017 139 (11), 4107-4116 DOI: 10.1021/jacs.6b13223
Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:74524
Deposited By: Tony Diaz
Deposited On:24 Feb 2017 18:45
Last Modified:09 Mar 2020 13:19

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