Electronic spectroscopy, photophysical properties, and emission quenching studies of an oxidatively robust perfluorinated platinum porphyrin

被引:80
作者
Lai, SW
Hou, YJ
Che, CM
Pang, HL
Wong, KY
Chang, CK
Zhu, NY
机构
[1] Univ Hong Kong, Inst Mol Technol Drug Discovery & Synth, Dept Chem, Hong Kong, Hong Kong, Peoples R China
[2] Univ Hong Kong, Inst Mol Technol Drug Discovery & Synth, Open Lab Chem Biol, Hong Kong, Hong Kong, Peoples R China
[3] Hong Kong Polytech Univ, Dept Appl Biol & Chem Technol, Kowloon, Hong Kong, Peoples R China
[4] Hong Kong Univ Sci & Technol, Dept Chem, Kowloon, Hong Kong, Peoples R China
关键词
D O I
10.1021/ic049902h
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The highly electron-deficient, beta-octafluorinated meso-tetrakis(pentafluorophenyl)-porphyrin (H2F28TPP) was metalated with platinum to afford the oxidatively robust luminophore [PtF28TPP], and its X-ray structure shows that the porphyrin core exists in a slightly saddle-shaped conformation. The absorption spectrum of [PtF28TPP] in CH2Cl2 displays a near-UV Soret band (B) at 383 nm (epsilon = 2.85 x 10(5) dm(3) mol(-1) cm(-1)) and two visible 0(1,0) and Q(0,0) bands at 501 (epsilon = 1.45 x 10(4) dm(3) Mol(-1) cm(-1)) and 533 (6 = 1.36 x 10(4) dml mol(-1) cm(-1)) nm, respectively. These absorption bands of [PtF28TPP] are blue-shifted from those in [PtF20TPP] (390, 504, and 538 nm, respectively) and [PtTPP] (401, 509, and 539 nm, respectively). Excitation of [PtF28TPP] (complex concentration = 1.5 x 10(-6) Mol dm(-3)) in dichloromethane at the Soret or Q(1,0) or Q(0,0) band gave a phosphorescence with peak maximum at 650 nm (lifetime = 5.8 mus) and a weak shoulder at 712 nm. Both the emission lifetime and quantum yield vary with solvent polarity, and plots of tau versus E-K and Phi versus E-K (where EK is the empirical solvent polarity parameter based on the hypsochromic shift of the longest wavelength absorption of the [Mo(CO)(4){(C5H4N)HC=NCH2C6H5}] complex with increasing solvent polarity; see: Kamlet, M. J.; Abboud, J. L. M.; Taft, R. W. Prog. Phys. Org. Chem, 1981, 13, pp 485-630) show linear correlation, indicating that the emission is sensitive to the local environment/medium, Electrochemical studies on [PtF28TPP] by cyclic voltammetry showed no porphyrin-centered oxidation at potential less than or equal to 1.5 V versus Ag/AgNO3, demonstrating that [PtF28TPP] is more resistant toward oxidation than [PtF20-TPP] (E-1/2 = 1.33 V) and [PtTPP] (E-1/2 = 0.97 V). The porphyrin-centered reduction of [PtF28TPP] occurs at -0.75 and -1.18 V, which is anodically shifted from those at -1.06 and -1.55 V in [PtF20TPP], and -1.51 V in [PtTPP], respectively. The excited-state reduction potential of [PtF28TPP] is estimated to be 1.49 V versus Ag/AgNO3. Over 97% of the emission intensity of [PtF28TPP] was retained after irradiation with a high power mercury arc lamp (500 W) for 14 h, compared to 90% and 12% for [PtF20TPP] and [PtTPP], respectively; hence, [PtF28TPP] exhibits superior photostability. Quenching of the emission of [PtF28TPP] by oxygen, alcohol, catechol, and butylamine reveals that [PtF28TPP] is an oxidatively robust material with medium-sensitive photoluminescence properties.
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页码:3724 / 3732
页数:9
相关论文
共 56 条
[1]   APPLICATION OF DIFFUSION CELLS TO THE PRODUCTION OF KNOWN CONCENTRATIONS OF GASEOUS HYDROCARBONS [J].
ALTSHULLER, AP ;
COHEN, IR .
ANALYTICAL CHEMISTRY, 1960, 32 (07) :802-810
[2]   BIS(BENZONITRILE)DICHLORO COMPLEXES OF PALLADIUM AND PLATINUM [J].
ANDERSON, GK ;
LIN, M .
INORGANIC SYNTHESES, 1990, 28 :60-63
[3]   Highly efficient phosphorescent emission from organic electroluminescent devices [J].
Baldo, MA ;
O'Brien, DF ;
You, Y ;
Shoustikov, A ;
Sibley, S ;
Thompson, ME ;
Forrest, SR .
NATURE, 1998, 395 (6698) :151-154
[4]   CRYSTALLOGRAPHIC AND EXAFS STUDIES OF CONFORMATIONALLY DESIGNED NONPLANAR NICKEL(II) PORPHYRINS [J].
BARKIGIA, KM ;
RENNER, MW ;
FURENLID, LR ;
MEDFORTH, CJ ;
SMITH, KM ;
FAJER, J .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (09) :3627-3635
[5]   MODULATION OF VALENCE ORBITAL LEVELS OF METALLOPORPHYRINS BY BETA-SUBSTITUTION - EVIDENCE FROM SPECTROSCOPIC AND ELECTROCHEMICAL STUDIES OF 2-SUBSTITUTED METALLO-5,10,15,20-TETRAPHENYLPORPHYRINS [J].
BINSTEAD, RA ;
CROSSLEY, MJ ;
HUSH, NS .
INORGANIC CHEMISTRY, 1991, 30 (06) :1259-1264
[6]   ELECTRONIC-STRUCTURES OF HALOGENATED RUTHENIUM PORPHYRINS - CRYSTAL-STRUCTURE OF RUTFPPCL8(CO)H2O (TFPPCL8=OCTA-BETA-CHLOROTETRAKIS(PENTAFLUOROPHENYL)PORPHYRIN) [J].
BIRNBAUM, ER ;
SCHAEFER, WP ;
LABINGER, JA ;
BERCAW, JE ;
GRAY, HB .
INORGANIC CHEMISTRY, 1995, 34 (07) :1751-1755
[7]   F-19 NMR-SPECTRA AND STRUCTURES OF HALOGENATED PORPHYRINS [J].
BIRNBAUM, ER ;
HEDGE, JA ;
GRINSTAFF, MW ;
SCHAEFER, WP ;
HENLING, L ;
LABINGER, JA ;
BERCAW, JE ;
GRAY, HB .
INORGANIC CHEMISTRY, 1995, 34 (14) :3625-3632
[8]   CYANOPORPHYRINS - COORDINATING AND ELECTROCHEMICAL PROPERTIES [J].
CALLOT, HJ ;
GIRAUDEAU, A ;
GROSS, M .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1975, (12) :1321-1324
[9]   NIH SHIFT IN HAEMIN-IODOSYLBENZENE-MEDIATED HYDROXYLATIONS [J].
CHANG, CK ;
EBINA, F .
JOURNAL OF THE CHEMICAL SOCIETY-CHEMICAL COMMUNICATIONS, 1981, (15) :778-779
[10]   [meso-Tetrakis(pentafluorophenyl)porphyrinato]platinum(II) as an efficient, oxidation-resistant red phosphor:: spectroscopic properties and applications in organic light-emitting diodes [J].
Che, CM ;
Hou, YJ ;
Chan, MCW ;
Guo, JH ;
Liu, Y ;
Wang, Y .
JOURNAL OF MATERIALS CHEMISTRY, 2003, 13 (06) :1362-1366