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Volumn 112, Issue 49, 2008, Pages 19209-19216

Structural and photophysical properties of self-assembled porphyrin nanoassemblies organized by ethylene glycol derivatives

Author keywords

[No Author keywords available]

Indexed keywords

BATHOCHROMIC SHIFTS; COMPOSITE NANOPARTICLES; EXCITED TRIPLET STATE; FLUORESCENCE QUENCHING; GLYCOL DERIVATIVES; HIER-ARCHICAL CLUSTERING; HYDROGEN BONDINGS; LONG RODS; MICROMETER SCALE; MIXED H; NANO-ASSEMBLIES; PHOTO-PHYSICAL PROPERTIES; QUENCHING PROCESS; SELF-ASSEMBLED; SINGLET-SINGLET ANNIHILATIONS; SOLVENT MIXTURES; STACKING EFFECTS; TRIPLET-TRIPLET ANNIHILATIONS;

EID: 64349104046     PISSN: 19327447     EISSN: 19327455     Source Type: Journal    
DOI: 10.1021/jp805202y     Document Type: Article
Times cited : (50)

References (124)
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    • 2P composites may be also due to the different solubilities between EGDE and TriEG toward a mixed solvent.
    • 2P composites may be also due to the different solubilities between EGDE and TriEG toward a mixed solvent.
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    • -1) are derived from hydroxyl groups of EG surfactants.
    • -1) are derived from hydroxyl groups of EG surfactants.
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    • We have searched the published crystal structures of H 2P(CO2H)4 including its solvent clathrates. The XRD patterns of H2P(CO2H)4 nanoassemblies are significantly different from ones simulated from the reported crystal structures other than one obtained by Goldberg et al. Therefore, it can be concluded that the H2P(CO2H)4 nanoassemblies have the similar crystal structure described by Goldberg et al. We analyzed by compound 1 in the following reference paper. See the reference paper: George, S, Lipstman, S, Muniappan, S, Goldberg, I. Cryst. Eng. Comm. 2006, 8, 417
    • 4 nanoassemblies have the similar crystal structure described by Goldberg et al. We analyzed by compound 1 in the following reference paper. See the reference paper: George, S.; Lipstman, S.; Muniappan, S.; Goldberg, I. Cryst. Eng. Comm. 2006, 8, 417.
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    • 4 moieties as reported in ref 23. Considering the standard set-up of XRD measurement and observed monoclinic unit structure (dihedral angles: 90° in axes a-b and b-c), such head-to-tail type interactions mainly occur in the internal structure. The XRD pattern and detail structures based on the results of the paper in ref 23 are shown in Supporting Information S4.
    • 4 moieties as reported in ref 23. Considering the standard set-up of XRD measurement and observed monoclinic unit structure (dihedral angles: 90° in axes a-b and b-c), such head-to-tail type interactions mainly occur in the internal structure. The XRD pattern and detail structures based on the results of the paper in ref 23 are shown in Supporting Information S4.
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    • 4/EG composite within a nanoparticle may be changeable because of the different spacer lengths of surfactants. However, the basic orientation trend appears to be similar based on XRD results.
    • 4/EG composite within a nanoparticle may be changeable because of the different spacer lengths of surfactants. However, the basic orientation trend appears to be similar based on XRD results.
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    • Although the similar fluorescence quenching properties relative to the monomeric form are observed in porphyrin aggregated systems (see refs 2c, 11c, d and 19e, the opposite case is also reported. For example, An and coworkers report that fluorescence intensity of organic nanoparticles composed of CN-MBE [1-cyano-trans-1,2-bis-(4'-methylbiphenyl)ethylene] is increased by almost 700 times in the nanoparticles. The enhanced emission in CN-MBE nanoparticles is attributed to the synergetic effect of intramolecular planarization and J-type aggregate formation in nanoparticles. See the reference paper: An, B. K, Kwon, S. K, Jung, S. D, Park, S. Y. J. Am. Chem. Soc. 2002, 124, 14410
    • Although the similar fluorescence quenching properties relative to the monomeric form are observed in porphyrin aggregated systems (see refs 2c, 11c, d and 19e), the opposite case is also reported. For example, An and coworkers report that fluorescence intensity of organic nanoparticles composed of CN-MBE [1-cyano-trans-1,2-bis-(4'-methylbiphenyl)ethylene] is increased by almost 700 times in the nanoparticles. The enhanced emission in CN-MBE nanoparticles is attributed to the synergetic effect of intramolecular planarization and J-type aggregate formation in nanoparticles. See the reference paper: An, B. K.; Kwon, S. K.; Jung, S. D.; Park, S. Y. J. Am. Chem. Soc. 2002, 124, 14410.
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    • 4 is set to 0.82 ns.
    • 4 is set to 0.82 ns.
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    • 4/EG composite nanoparticles are very similar as discussed in Figure 4. Therefore, the reason for a trend of decreased lifetimes may be attributable to the decreased range of exciton motion with decreasing particle-sizes within a nanoparticle. The similar trend is also reported by Nakanishi and co-workers. See the following paper: Kasai, H.; Kamatani, H.; Yoshikawa, Y.; Okada, S.; Oikawa, H.; Watanabe, A.; Itoh, O.; Nakanishi, H. Chem. Lett. 1997, 26, 1181.
    • 4/EG composite nanoparticles are very similar as discussed in Figure 4. Therefore, the reason for a trend of decreased lifetimes may be attributable to the decreased range of exciton motion with decreasing particle-sizes within a nanoparticle. The similar trend is also reported by Nakanishi and co-workers. See the following paper: Kasai, H.; Kamatani, H.; Yoshikawa, Y.; Okada, S.; Oikawa, H.; Watanabe, A.; Itoh, O.; Nakanishi, H. Chem. Lett. 1997, 26, 1181.
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    • The difference between ?S and ?T may be dependent on the freedom degree of exciton motion of excited singlet or triplet state in the crystalline structures. Although in the short-lived singlet state, excitons move freely within the crystalline structure (free excitons), excitons are likely trapped by some defects because of its relatively long lifetime in the triplet state (trapped excitons). Yokoi and Ohba reported that T-T annihilation between free and trapped triplet excitons occurs much faster due to the long-range interaction comparing to the one between two free excitons. Careful screening of the difference in our system is currently underway. See the reference paper: Yokoi, K.; Ohba, Y. J. Chem. Phys. 1987, 86, 3318.
    • The difference between ?S and ?T may be dependent on the freedom degree of exciton motion of excited singlet or triplet state in the crystalline structures. Although in the short-lived singlet state, excitons move freely within the crystalline structure (free excitons), excitons are likely trapped by some defects because of its relatively long lifetime in the triplet state (trapped excitons). Yokoi and Ohba reported that T-T annihilation between free and trapped triplet excitons occurs much faster due to the long-range interaction comparing to the one between two free excitons. Careful screening of the difference in our system is currently underway. See the reference paper: Yokoi, K.; Ohba, Y. J. Chem. Phys. 1987, 86, 3318.


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