• Bulletin of the Korean Chemical Society
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• 제29권7호
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• pp.1353-1358
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• 2008

Benzyl arylether dendrimers with zinc porphyrin core and terminal vinyl groups have been synthesized and their photophysical properties and the influence of dendritic environments were investigated. Free base porphyrin-cored benzyl arylether dendrimers 1a-1c and 3a-3c, and their zinc derivatives 2a-2c and 4a-4c have been prepared. Absorption spectra are similar for all porphyrin-cored benzyl arylether dendrimers, except that absorption intensity at 280 nm increases in the higher generation of dendrimer. Fluorescence spectra are similar with two bands for all free base porphyrin dendrimers 1a-1c and 3a-3c, although fluorescence intensity ratio of shorter wavelength emission band to longer wavelength band varies with the generation of dendrimer. Emission efficiencies of 1a-1c and 3a-3c are lower than that of TTP. Emission efficiencies of 2a-2c and 4a-4c are higher than that of ZnTTP. Absorption and emission properties of 1a-1c, 2a-2c, 3a-3c, and 4a-4c were affected negligibly with dendritic environments.

• Bulletin of the Korean Chemical Society
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• 제29권4호
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• pp.761-766
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• 2008

Photoresponsive arylether dendrimers Bis-azo-Gn(3,5) 1a-1c and Bis-azo-Gn(3,4,5) 2a-2c (n = 1-3) with an azobenzene unit at the core and several vinyl groups (3,5-bis(but-3-enyloxy)phenyl groups or 3,4,5-tris(but-3- enyloxy)phenyl groups) at the periphery have been prepared. Their structures and reversible trans-cis isomerization behaviors have been investigated by $^1H$-NMR, $^{13}C$-NMR, MALDI-TOF-Mass, and UV-vis spectra. All six azobenzene-cored dendrimers carried out very fast trans $\rightarrow$ cis photoisomerization on irradiation of 350 nm light and reached to the photostationary state within 180 s. During the dark incubation, slow thermal back reversion from cis to trans form is observed for all six dendrimers and is completed within 3 days for 1a-1c and 1 day for 2a-2c. Isomerization efficiency decreases with increasing generation. However, the initial reaction rates of both trans $\rightarrow$ cis photochemical isomerization and cis $\rightarrow$ trans thermal isomerization increases significantly with increasing generation for dendrimers for 1a-1c but only slightly for 2a-2c.

• Bulletin of the Korean Chemical Society
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• 제32권12호
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• pp.4247-4252
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• 2011

The porphyrin-incorporated arylether dendrimers ZnP-D1 and ZnP-D4 were investigated to discover the influence of dendritic environments for the axial ligation of pyridine and photoinduced electron transfer by methyl viologen. Absorption and fluorescence spectra of ZnP, ZnP-D1, and ZnP-D4 were measured in dichloromethane with the addition of pyridine or methyl viologen dichloride. Axial ligation of pyridine was confirmed by red-shifted absorption spectrum. The complex formation constants $K_f$ (Table 1) for axial coordination of pyridine on ZnP, ZnP-D1, and ZnP-D4 were estimated to be $4.4{\times}10^3\;M^{-1}$, $3.3{\times}10^3\;M^{-1}$, and $1.7{\times}10^3\;M^{-1}$, respectively. The photoinduced electron transfer to methyl viologen dichloride was confirmed by fluorescence quenching. Stern-Volmer constants Ksv for ZnP, ZnP-D1, and ZnP-D4 were calculated to be $2.6{\times}10^3$, $2.5{\times}10^3$, and $2.1{\times}10^3$, respectively. ZnP-D4 surrounded by 4 aryl ether dendrons shows the smallest $K_f$ and Ksv values, with comparison to ZnP and ZnP-D1.