Highly selective synthesis of the ring-B reduced chlorins by ferric chloride-mediated oxidation of bacteriochlorins: effects of the fused imide vs isocyclic ring on photophysical and electrochemical properties.
The oxidation of bacteriopyropheophorbide with ferric chloride hexahydrate or its anhydrous form produced the ring-D oxidized (ring-B reduced) chlorin in >95% yield. Replacing the five-member isocyclic ring in bacteriopyropheophorbide- a with a fused six-member N-butylimide ring system made no difference in regioselective oxidation, and the corresponding ring-B reduced chlorin was isolated in almost quantitative yield. When the oxidant was replaced by 2,3-dichloro-5,6-dicyano-p-benzoquinone, which is frequently used at the oxidizing stage of the porphyrin synthesis, the ring-B oxidized (ring-D reduced) chlorins were obtained. With both ring-B reduced and ring-D reduced chlorins in hand, their photophysical and electrochemical properties were examined and compared for the first time. The ring-B reduced chlorine 20, with a fused six-member N-butylimide ring, exhibits the most red-shifted absorption band (at lambda(max) = 746 nm), the lowest fluorescence quantum yield (4.5%), and the largest quantum yield of singlet oxygen formation (67%) among the reduced ring-B and ring-D chlorins investigated in this study. Measurements of the one-electron oxidation and reduction potentials show that compound 20 is also the easiest to oxidize among the examined compounds and the third easiest to reduce. In addition, the 1.62 eV HOMO-LUMO gap of 20 is the smallest of the examined compounds, and this agrees with values calculated using the DFT method. Spectroelectrochemical measurements afforded UV-visible absorption spectra for both the radical cations and radical anions of the examined chlorins. The ring-B reduced compound 20, with a fused six-member N-butylimide ring, is regarded as the most promising candidate in this study for photodynamic therapy because it has the longest wavelength absorption and the largest quantum yield of singlet oxygen formation among the compounds investigated.
Liu
Chao
C
Chemistry Division, PDT Center, Cell Stress Biology, Roswell Park Cancer Institute, Buffalo, New York 14263, USA.
Dobhal
Mahabeer P
MP
Ethirajan
Manivannan
M
Missert
Joseph R
JR
Pandey
Ravindra K
RK
Balasubramanian
Sathyamangalam
S
Sukumaran
Dinesh K
DK
Zhang
Min
M
Kadish
Karl M
KM
Ohkubo
Kei
K
Fukuzumi
Shunichi
S
D025541:Bacteriochlorophyll A / Q000737:chemistry*; D002712:Chlorides; D002942:Circular Dichroism / Q000379:methods; D003198:Computer Simulation; D004563:Electrochemistry; D005290:Ferric Compounds / Q000737:chemistry*; D007094:Imides / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy / Q000379:methods / Q000592:standards; D008956:Models, Chemical; D008968:Molecular Conformation; D010084:Oxidation-Reduction; D010777:Photochemistry; D011166:Porphyrins / Q000138:chemical synthesis* / Q000737:chemistry*; D011789:Quantum Theory; D012015:Reference Standards; D026082:Singlet Oxygen / Q000737:chemistry; D013050:Spectrometry, Fluorescence / Q000379:methods; D013237:Stereoisomerism
D025541:Bacteriochlorophyll A; D002712:Chlorides; D005290:Ferric Compounds; D007094:Imides; D011166:Porphyrins; C452433:bacteriochlorin; D026082:Singlet Oxygen; C006969:chlorin; C024555:ferric chloride