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. Both1H 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 the1*ExBIPY2+ unit to the DAPP2+ unit in 0.5 ps to yield1*DAPP2+. The same excitation wavelength simultaneously populates a higher excited state of1*DAPP2+ which then undergoes ultrafast intramolecular electron transfer from1*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.
| Original language | English |
|---|---|
| Pages (from-to) | 4107-4116 |
| Number of pages | 10 |
| Journal | Journal of the American Chemical Society |
| Volume | 139 |
| Issue number | 11 |
| DOIs | |
| Publication status | Published - Mar 22 2017 |
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ASJC Scopus subject areas
- Catalysis
- Chemistry(all)
- Biochemistry
- Colloid and Surface Chemistry
Cite this
Intramolecular Energy and Electron Transfer within a Diazaperopyrenium-Based Cyclophane. / 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, William A.; Farha, Omar K.; Hupp, Joseph T; Wasielewski, Michael R; Stoddart, J. Fraser.
In: Journal of the American Chemical Society, Vol. 139, No. 11, 22.03.2017, p. 4107-4116.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Intramolecular Energy and Electron Transfer within a Diazaperopyrenium-Based Cyclophane
AU - Gong, Xirui
AU - Young, Ryan M.
AU - Hartlieb, Karel J.
AU - Miller, Claire
AU - Wu, Yilei
AU - Xiao, Hai
AU - Li, Peng
AU - Hafezi, Nema
AU - Zhou, Jiawang
AU - Ma, Lin
AU - Cheng, Tao
AU - Goddard, William A.
AU - Farha, Omar K.
AU - Hupp, Joseph T
AU - Wasielewski, Michael R
AU - Stoddart, J. Fraser
PY - 2017/3/22
Y1 - 2017/3/22
N2 - 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. Both1H 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 the1*ExBIPY2+ unit to the DAPP2+ unit in 0.5 ps to yield1*DAPP2+. The same excitation wavelength simultaneously populates a higher excited state of1*DAPP2+ which then undergoes ultrafast intramolecular electron transfer from1*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.
AB - 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. Both1H 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 the1*ExBIPY2+ unit to the DAPP2+ unit in 0.5 ps to yield1*DAPP2+. The same excitation wavelength simultaneously populates a higher excited state of1*DAPP2+ which then undergoes ultrafast intramolecular electron transfer from1*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.
UR - http://www.scopus.com/inward/record.url?scp=85016158725&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=85016158725&partnerID=8YFLogxK
U2 - 10.1021/jacs.6b13223
DO - 10.1021/jacs.6b13223
M3 - Article
AN - SCOPUS:85016158725
VL - 139
SP - 4107
EP - 4116
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 11
ER -