Abstract
A bisindole-bridged-porphyrin tweezer (1), a pair of zinc porphyrins (PZn's) connected to bisindole bridge (BB) via the Cu I-mediated alkyne-azide click chemistry, exhibited unique switching in forward and backward photoinduced energy transfer by specific guest bindings. The addition of Cu2+ caused a change in electronic absorption and fluorescence quenching of 1. MALDI-TOF-MS and FT-IR analyses indicated the formation of stable coordination complex between 1 and Cu2+ (1-Cu(II)). Without Cu2+ coordination, the excitation energy flows from BB to PZn's with significantly high energy transfer efficiency. In contrast, the direction of energy flow in 1 was completely reversed by the coordination of Cu2+. The difference in fluorescence quantum yield between 1 and 1-Cu(II) indicates that more than 95% of excitation energy of PZn flows into Cu(II)-coordinated BB. The energy transfer efficiency was further controlled by bidentate ligand coordination onto 1-Cu(II). When pyrophosphate ion was added to 1-Cu(II), the recovery of fluorescence emission from PZn was observed. The quantum mechanical calculations indicated that the Cu(II)-coordinated BB has square planar geometry, which can be distorted to form octahedral geometry due to the coordination of bidentate ligands.
| Original language | English |
|---|---|
| Pages (from-to) | 1672-1679 |
| Number of pages | 8 |
| Journal | Journal of the American Chemical Society |
| Volume | 136 |
| Issue number | 4 |
| DOIs | |
| Publication status | Published - 2014 Jan 29 |
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All Science Journal Classification (ASJC) codes
- Catalysis
- Chemistry(all)
- Biochemistry
- Colloid and Surface Chemistry
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A porphyrin-based molecular tweezer : Guest-induced switching of forward and backward photoinduced energy transfer. / Yoon, Hongsik; Lim, Jong Min; Gee, Hyuk Chan; Lee, Chi Hwa; Jeong, Young Hwan; Kim, Dongho; Jang, Woo Dong.
In: Journal of the American Chemical Society, Vol. 136, No. 4, 29.01.2014, p. 1672-1679.Research output: Contribution to journal › Article
TY - JOUR
T1 - A porphyrin-based molecular tweezer
T2 - Guest-induced switching of forward and backward photoinduced energy transfer
AU - Yoon, Hongsik
AU - Lim, Jong Min
AU - Gee, Hyuk Chan
AU - Lee, Chi Hwa
AU - Jeong, Young Hwan
AU - Kim, Dongho
AU - Jang, Woo Dong
PY - 2014/1/29
Y1 - 2014/1/29
N2 - A bisindole-bridged-porphyrin tweezer (1), a pair of zinc porphyrins (PZn's) connected to bisindole bridge (BB) via the Cu I-mediated alkyne-azide click chemistry, exhibited unique switching in forward and backward photoinduced energy transfer by specific guest bindings. The addition of Cu2+ caused a change in electronic absorption and fluorescence quenching of 1. MALDI-TOF-MS and FT-IR analyses indicated the formation of stable coordination complex between 1 and Cu2+ (1-Cu(II)). Without Cu2+ coordination, the excitation energy flows from BB to PZn's with significantly high energy transfer efficiency. In contrast, the direction of energy flow in 1 was completely reversed by the coordination of Cu2+. The difference in fluorescence quantum yield between 1 and 1-Cu(II) indicates that more than 95% of excitation energy of PZn flows into Cu(II)-coordinated BB. The energy transfer efficiency was further controlled by bidentate ligand coordination onto 1-Cu(II). When pyrophosphate ion was added to 1-Cu(II), the recovery of fluorescence emission from PZn was observed. The quantum mechanical calculations indicated that the Cu(II)-coordinated BB has square planar geometry, which can be distorted to form octahedral geometry due to the coordination of bidentate ligands.
AB - A bisindole-bridged-porphyrin tweezer (1), a pair of zinc porphyrins (PZn's) connected to bisindole bridge (BB) via the Cu I-mediated alkyne-azide click chemistry, exhibited unique switching in forward and backward photoinduced energy transfer by specific guest bindings. The addition of Cu2+ caused a change in electronic absorption and fluorescence quenching of 1. MALDI-TOF-MS and FT-IR analyses indicated the formation of stable coordination complex between 1 and Cu2+ (1-Cu(II)). Without Cu2+ coordination, the excitation energy flows from BB to PZn's with significantly high energy transfer efficiency. In contrast, the direction of energy flow in 1 was completely reversed by the coordination of Cu2+. The difference in fluorescence quantum yield between 1 and 1-Cu(II) indicates that more than 95% of excitation energy of PZn flows into Cu(II)-coordinated BB. The energy transfer efficiency was further controlled by bidentate ligand coordination onto 1-Cu(II). When pyrophosphate ion was added to 1-Cu(II), the recovery of fluorescence emission from PZn was observed. The quantum mechanical calculations indicated that the Cu(II)-coordinated BB has square planar geometry, which can be distorted to form octahedral geometry due to the coordination of bidentate ligands.
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U2 - 10.1021/ja4124048
DO - 10.1021/ja4124048
M3 - Article
AN - SCOPUS:84893488638
VL - 136
SP - 1672
EP - 1679
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 4
ER -