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, 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 excitedmore »
- Authors:
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[1];
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;
[1];
[1];
[2];
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- Materials and Process Simulation Center, California Institute of Technology, Pasadena, California 91125, United States
- 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)
- 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. https://doi.org/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. https://doi.org/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 = {Fri Mar 10 00:00:00 EST 2017},
month = {Fri Mar 10 00:00:00 EST 2017}
}
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https://doi.org/10.1021/jacs.6b13223
https://doi.org/10.1021/jacs.6b13223
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Cited by: 32 works
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Figures / Tables:
Figure 1: Structural formulas of (a) PDI, (b) ExBIPY2+, (c) DAPP2+, and (d) DAPPBox4+.
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Works referencing / citing this record:
CCDC 1480961: Experimental Crystal Structure Determination: TAVLOU : 9,16,39,46-tetra-azoniatridecacyclo[44.2.2.22,5.26,9.211,14.241,44.116,24.131,39.018,23.021,34.022,27.028,33.032,37]hexaconta-1(48),2,4,6,8,11,13,16(54),17,19,21,23,25,27,29,31(53),32(37),33,35,38,41,43,46,49,51,55,57,59-octacosaene tetrakis(trifluoroacetate) unknown solvate
Space Group: P 1 (2), Cell: a 13.3141(7)Å b 21.1146(10)Å c 23.4964(13)Å, α 96.654(4)° β 99.661(4)° γ 105.932(4)°
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Versatile and Switchable Responsive Properties of a Lanthanide‐Viologen Metal–Organic Framework
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- Small, Vol. 15, Issue 5
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Guest recognition enhanced by lateral interactions
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