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Title: Intramolecular Energy and Electron Transfer within a Diazaperopyrenium-Based Cyclophane

Abstract

Molecules capable of performing highly efficient energy transfer and ultrafast photoinduced electron transfer in well-defined multichromophoric structures are indispensable to the development of artificial photofunctional 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+. Asmore » a result, 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.« less

Authors:
; ORCiD logo; ; ; ; ORCiD logo [1]; ORCiD logo; ; ORCiD logo; ; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo; ORCiD logo; ORCiD logo
  1. Materials and Process Simulation Center, California Institute of Technology, Pasadena, California 91125, United States
  2. Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah 22254, Saudi Arabia
Publication Date:
Research Org.:
Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1346430
Alternate Identifier(s):
OSTI ID: 1351622
Grant/Contract Number:  
FG02 87ER13808; FG02-99ER14999
Resource Type:
Published Article
Journal Name:
Journal of the American Chemical Society
Additional Journal Information:
Journal Name: Journal of the American Chemical Society Journal Volume: 139 Journal Issue: 11; Journal ID: ISSN 0002-7863
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE

Citation Formats

Gong, Xirui, Young, Ryan M., Hartlieb, Karel J., Miller, Claire, Wu, Yilei, Xiao, Hai, Li, Peng, Hafezi, Nema, Zhou, Jiawang, Ma, Lin, Cheng, Tao, Goddard, III, William A., Farha, Omar K., Hupp, Joseph T., Wasielewski, Michael R., and Stoddart, J. Fraser. Intramolecular Energy and Electron Transfer within a Diazaperopyrenium-Based Cyclophane. United States: N. p., 2017. Web. doi:10.1021/jacs.6b13223.
Gong, Xirui, Young, Ryan M., Hartlieb, Karel J., Miller, Claire, Wu, Yilei, Xiao, Hai, Li, Peng, Hafezi, Nema, Zhou, Jiawang, Ma, Lin, Cheng, Tao, Goddard, III, William A., Farha, Omar K., Hupp, Joseph T., Wasielewski, Michael R., & Stoddart, J. Fraser. Intramolecular Energy and Electron Transfer within a Diazaperopyrenium-Based Cyclophane. United States. doi:10.1021/jacs.6b13223.
Gong, Xirui, Young, Ryan M., Hartlieb, Karel J., Miller, Claire, Wu, Yilei, Xiao, Hai, Li, Peng, Hafezi, Nema, Zhou, Jiawang, Ma, Lin, Cheng, Tao, Goddard, III, William A., Farha, Omar K., Hupp, Joseph T., Wasielewski, Michael R., and Stoddart, J. Fraser. Fri . "Intramolecular Energy and Electron Transfer within a Diazaperopyrenium-Based Cyclophane". United States. doi:10.1021/jacs.6b13223.
@article{osti_1346430,
title = {Intramolecular Energy and Electron Transfer within a Diazaperopyrenium-Based Cyclophane},
author = {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, III, William A. and Farha, Omar K. and Hupp, Joseph T. and Wasielewski, Michael R. and Stoddart, J. Fraser},
abstractNote = {Molecules capable of performing highly efficient energy transfer and ultrafast photoinduced electron transfer in well-defined multichromophoric structures are indispensable to the development of artificial photofunctional systems. Herein, we report on the synthesis, characterization, and photophysical properties of a rationally designed multichromophoric tetracationic cyclophane, DAPPBox4+, containing a diazaperopyrenium (DAPP2+) unit and an extended viologen (ExBIPY2+) 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, DAPPBox4+. The solid-state superstructure of this cyclophane reveals a herringbone-type packing motif, leading to two types of π···π interactions: (i) between the ExBIPY2+ unit and the DAPP2+ unit (π···π distance of 3.7 Å) in the adjacent parallel cyclophane, as well as (ii) between the ExBIPY2+ 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 DAPPBox4+ at 330 nm, rapid and quantitative intramolecular energy transfer occurs from the 1*ExBIPY2+ unit to the DAPP2+ unit in 0.5 ps to yield 1*DAPP2+. As a result, the same excitation wavelength simultaneously populates a higher excited state of 1*DAPP2+ which then undergoes ultrafast intramolecular electron transfer from 1*DAPP2+ to ExBIPY2+ to yield the DAPP3+•–ExBIPY+• radical ion pair in τ = 1.5 ps. Selective excitation of DAPP2+ at 505 nm populates a lower excited state where electron transfer is kinetically unfavorable.},
doi = {10.1021/jacs.6b13223},
journal = {Journal of the American Chemical Society},
number = 11,
volume = 139,
place = {United States},
year = {2017},
month = {3}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1021/jacs.6b13223

Citation Metrics:
Cited by: 3 works
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Figures / Tables:

Figure 1 Figure 1: Structural formulas of (a) PDI, (b) ExBIPY2+, (c) DAPP2+, and (d) DAPPBox4+.

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journal, October 2017

  • Kumar, Rajesh; Semwal, Shrivats; Choudhury, Joyanta
  • Chemistry - A European Journal, Vol. 23, Issue 60
  • DOI: 10.1002/chem.201703781

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journal, January 2019


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journal, January 2019

  • Zhou, Jiawang; Wu, Yilei; Roy, Indranil
  • Chemical Science, Vol. 10, Issue 15
  • DOI: 10.1039/c8sc05514a

Guest recognition enhanced by lateral interactions
journal, January 2019

  • Jiao, Tianyu; Cai, Kang; Liu, Zhichang
  • Chemical Science, Vol. 10, Issue 19
  • DOI: 10.1039/c9sc00591a