Abstract
Three coumarin derivatives (7-propoxy coumarin, coumarin-480, and coumarin-540a, 2, 3, and 4, respectively) having different absorption and emission spectra were encapsulated within a water-soluble organic capsule formed by the two positively charged ammonium-functionalized cavitand octaamine (OAm, 1). Guests 2, 3, and 4 absorb in ultraviolet, violet, and blue regions and emit in violet, blue, and green regions, respectively. Energy transfer between the above three coumarin@(OAm)2 complexes assembled on the surface of a saponite clay nanosheet was investigated by steady-state and time-resolved emission techniques. Judging from their emission and excitation spectra, we concluded that the singlet-singlet energy transfer proceeded from 2 to 3, from 2 to 4, and from 3 to 4 when OAm-encapsulated 2, 3, and 4 were aligned on a clay surface as two-component systems. Under such conditions, the energy transfer efficiencies for the paths 2∗ to 3, 2∗ to 4, and 3∗ to 4 were calculated to be 33, 36, and 50% in two-component systems. When all three coumarins were assembled on the surface and 2 was excited, the energy transfer efficiencies for the paths 2∗ to 3, 2∗ to 4, and 3∗ to 4 were estimated to be 32, 34, and 33%. A comparison of energy transfer efficiencies of the two-component and three-component systems revealed that excitation of 2 leads to emission from 4. Successful merging of supramolecular chemistry and surface chemistry by demonstrating novel multi-step energy transfer in a three-component dye encapsulated system on a clay surface opens up newer opportunities for exploring such systems in an artificial light-harvesting phenomenon.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 2920-2927 |
| Number of pages | 8 |
| Journal | Langmuir |
| Volume | 32 |
| Issue number | 12 |
| DOIs | |
| State | Published - Mar 29 2016 |
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ASJC Scopus subject areas
- Electrochemistry
- Condensed Matter Physics
- Surfaces and Interfaces
- Materials Science(all)
- Spectroscopy
Cite this
Supramolecular Surface Photochemistry : Cascade Energy Transfer between Encapsulated Dyes Aligned on a Clay Nanosheet Surface. / Tsukamoto, Takamasa; Ramasamy, Elamparuthi; Shimada, Tetsuya; Takagi, Shinsuke; Ramamurthy, Vaidhyanathan.
In: Langmuir, Vol. 32, No. 12, 29.03.2016, p. 2920-2927.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Supramolecular Surface Photochemistry
T2 - Cascade Energy Transfer between Encapsulated Dyes Aligned on a Clay Nanosheet Surface
AU - Tsukamoto, Takamasa
AU - Ramasamy, Elamparuthi
AU - Shimada, Tetsuya
AU - Takagi, Shinsuke
AU - Ramamurthy, Vaidhyanathan
PY - 2016/3/29
Y1 - 2016/3/29
N2 - Three coumarin derivatives (7-propoxy coumarin, coumarin-480, and coumarin-540a, 2, 3, and 4, respectively) having different absorption and emission spectra were encapsulated within a water-soluble organic capsule formed by the two positively charged ammonium-functionalized cavitand octaamine (OAm, 1). Guests 2, 3, and 4 absorb in ultraviolet, violet, and blue regions and emit in violet, blue, and green regions, respectively. Energy transfer between the above three coumarin@(OAm)2 complexes assembled on the surface of a saponite clay nanosheet was investigated by steady-state and time-resolved emission techniques. Judging from their emission and excitation spectra, we concluded that the singlet-singlet energy transfer proceeded from 2 to 3, from 2 to 4, and from 3 to 4 when OAm-encapsulated 2, 3, and 4 were aligned on a clay surface as two-component systems. Under such conditions, the energy transfer efficiencies for the paths 2∗ to 3, 2∗ to 4, and 3∗ to 4 were calculated to be 33, 36, and 50% in two-component systems. When all three coumarins were assembled on the surface and 2 was excited, the energy transfer efficiencies for the paths 2∗ to 3, 2∗ to 4, and 3∗ to 4 were estimated to be 32, 34, and 33%. A comparison of energy transfer efficiencies of the two-component and three-component systems revealed that excitation of 2 leads to emission from 4. Successful merging of supramolecular chemistry and surface chemistry by demonstrating novel multi-step energy transfer in a three-component dye encapsulated system on a clay surface opens up newer opportunities for exploring such systems in an artificial light-harvesting phenomenon.
AB - Three coumarin derivatives (7-propoxy coumarin, coumarin-480, and coumarin-540a, 2, 3, and 4, respectively) having different absorption and emission spectra were encapsulated within a water-soluble organic capsule formed by the two positively charged ammonium-functionalized cavitand octaamine (OAm, 1). Guests 2, 3, and 4 absorb in ultraviolet, violet, and blue regions and emit in violet, blue, and green regions, respectively. Energy transfer between the above three coumarin@(OAm)2 complexes assembled on the surface of a saponite clay nanosheet was investigated by steady-state and time-resolved emission techniques. Judging from their emission and excitation spectra, we concluded that the singlet-singlet energy transfer proceeded from 2 to 3, from 2 to 4, and from 3 to 4 when OAm-encapsulated 2, 3, and 4 were aligned on a clay surface as two-component systems. Under such conditions, the energy transfer efficiencies for the paths 2∗ to 3, 2∗ to 4, and 3∗ to 4 were calculated to be 33, 36, and 50% in two-component systems. When all three coumarins were assembled on the surface and 2 was excited, the energy transfer efficiencies for the paths 2∗ to 3, 2∗ to 4, and 3∗ to 4 were estimated to be 32, 34, and 33%. A comparison of energy transfer efficiencies of the two-component and three-component systems revealed that excitation of 2 leads to emission from 4. Successful merging of supramolecular chemistry and surface chemistry by demonstrating novel multi-step energy transfer in a three-component dye encapsulated system on a clay surface opens up newer opportunities for exploring such systems in an artificial light-harvesting phenomenon.
UR - http://www.scopus.com/inward/record.url?scp=84962433699&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84962433699&partnerID=8YFLogxK
U2 - 10.1021/acs.langmuir.5b03962
DO - 10.1021/acs.langmuir.5b03962
M3 - Article
C2 - 26963843
AN - SCOPUS:84962433699
VL - 32
SP - 2920
EP - 2927
JO - Langmuir
JF - Langmuir
SN - 0743-7463
IS - 12
ER -