Synthesis and electronic properties of regioisomerically pure oxochlorins

被引:63
作者
Taniguchi, M
Kim, HJ
Ra, DY
Schwartz, JK
Kirmaier, C
Hindin, E
Diers, JR
Prathapan, S
Bocian, DF
Holten, D
Lindsey, JS
机构
[1] N Carolina State Univ, Dept Chem, Raleigh, NC 27695 USA
[2] Washington Univ, Dept Chem, St Louis, MO 63130 USA
[3] Univ Calif Riverside, Dept Chem, Riverside, CA 92521 USA
[4] Cochin Univ Sci & Technol, Dept Appl Chem, Cochin 682022, Kerala, India
关键词
D O I
10.1021/jo025843i
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
We describe a two-step conversion of C-alkylated zinc chlorins to zinc oxochlorins wherein the keto group is located in the reduced ring (17-position) of the macrocycle. The transformation proceeds by hydroxylation upon exposure to alumina followed by dehydrogenation with DDQ. The reactions are compatible with ethyne, iodo, ester, trimethylsilyl, and pentafluorophenyl groups. A route to a spirohexyl-substituted chlorin/oxochlorin has also been developed. Representative chlorins and oxochlorins were characterized by static and time-resolved absorption spectroscopy and fluorescence spectroscopy, resonance Raman spectroscopy, and electrochemistry. The fluorescence quantum yields of the zinc oxochlorins Phi(f) = 0.030-0.047) or free base (Fb) oxochlorins (Phi(f) = 0.13-0.16) are comparable to those of zinc tetraphenylporphyrin (ZnTPP) or free base tetraphenylporphyrin (FbTPP), respectively. The excited-state lifetimes of the zinc oxochlorins (r = 0.5-0.7 ns) are on average 4-fold lower than that of ZnTPP, and the lifetimes of the Fb oxochlorins (T = 7.4-8.9 ns) are similar to40% shorter than that of FbTPP. Time-resolved absorption spectroscopy of a zinc oxochlorin indicates the yield of intersystem crossing is >70%. Resonance Raman spectroscopy of copper oxochlorins show strong resonance enhancement of the keto group upon Soret excitation but not with Q(y)-band excitation, which is attributed to the location of the keto group in the reduced ring (rather than in the isocyclic ring as occurs in chlorophylls). The one-electron oxidation potential of the zinc oxochlorins is shifted to more positive potentials by approximately 240 mV compared with that of the zinc chlorin. Collectively, the fluorescence yields, excited-state lifetimes, oxidation potentials, and various spectral characteristics of the chlorin and oxochlorin building blocks provide the foundation for studies of photochemical processes in larger architectures based on these chromophores.
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页码:7329 / 7342
页数:14
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