Fluorescence and electrochemical properties of naphthylporphyrins and porphyrin–anthraquinone dyads

Tao, Minli; Zhou, Xueqin; Ma, Jianbiao; Liu, Dongzhi; Jian-wei, Xing

doi:10.1016/j.dyepig.2006.06.022

Cited by 16 publications

(7 citation statements)

References 16 publications

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“…We have calculated the electron affinity of the neutral porphyrin macrocycle to be 2.0 eV at the B3LYP/ 6-31Gϩϩ(d,p)//6-31Gϩ(d,p) level of theory, which is in accordance with work by others [31]. However, the Coulomb repulsion between the two excess charges likely renders the dianion unbound.…”

Section: Resultssupporting

confidence: 62%

Electron-capture—Induced dissociation of protoporphyrin IX ions

Bernigaud

Drenck

Huber

et al. 2008

J. Am. Soc. Mass Spectrom.

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Electron-capture induced dissociation of protoporphyrin cations and anions has been studied. The cations captured two electrons in two successive collisions and were converted to the corresponding even-electron anions. About one fifth of the ions lost a hydrogen atom to become radical anions but otherwise very little fragmentation was observed. The anions captured an electron to become dianions. No hydrogen loss occurred, and the only fragmentation channel observed was loss of CO2H, to give a doubly charged carbanion. Our results indicate that protoporphyrin ions are very efficient in accommodating one or even two electrons in the lowest unoccupied molecular orbital of the porphyrin macrocycle, and that electron capture induces only limited dissociation.

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Section: Resultssupporting

confidence: 62%

Electron-capture—Induced dissociation of protoporphyrin IX ions

Bernigaud

Drenck

Huber

et al. 2008

J. Am. Soc. Mass Spectrom.

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“…Nonmetalated, free-base, tetrapyrrolic porphyrins exhibit two stepwise, one-electron, reversible oxidations , and reduction reactions . In methylene chloride, dithiaporphyrin 3 displays four sets of quasi-reversible redox peaks, two one-electron oxidations, and two one-electron reductions as shown in Figure .…”

Section: Resultsmentioning

confidence: 99%

“…In addition, the difference between half-wave oxidation potentials of the radical cation and dication in our previous work was 0.20 V compared to 0.28 V for 3 , suggesting a destabilization of the dication caused by the introduction of the two pendant diester functionalities. The reported two, one-electron oxidation half-potentials for metal-free, tetraphenyl porphyrins (H 2 TPP) are 0.4 and 0.7 V versus Fc/Fc + , which is 230 mV less anodic for the first oxidation then 3 , which shows the replacement of two nitrogen heteroatoms with sulfurs within the aromatic core causes a stabilization of the HOMO energy. Dithiaporphyrin 3 was also shown to have two consecutive, one-electron reduction reactions at values similar to the analogous TP-N 2 S 2 (−1.44 V and −1.71 V vs versus Fc/Fc + ) measured under similar electrochemical conditions .…”

Section: Resultsmentioning

confidence: 99%

Synthesis and Optical and Electronic Properties of Core-Modified 21,23-Dithiaporphyrins

2013

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Core-modified 21,23-dithiaporphyrins, meso-substituted with both electron-withdrawing 4-phenylcarboxylic acids and related butyl esters, and electron-donating phenyldodecyl ethers were synthesized. The porphyrins displayed broad absorbance profiles that spanned from 400 to 800 nm with molar absorptivities ranging from 2500 to 200000 M(-1) cm(-1). Electrochemical experiments showed the dithiaporphyrins undergo two consecutive, one-electron, quasi-reversible oxidations and reductions at -1.78, -1.43, 0.63, and 0.91 V versus a ferrocene/ferrocenium internal standard. Spectroelectrochemistry and cyclic voltammetry revealed the dithiaporphyrins are stable and can endure many cycles of oxidation and reduction without signs of decomposition. The electronics of the two dithiaporphyrins were similar, and DFT calculations showed the HOMO-LUMO energy difference was smaller than tetrapyrrolic porphyrin analogues. Overall, the combination of desirable electronics, namely: quasi-reversible oxidations and reductions as well as broad absorbance profiles, combined with stability, imply that these core-modified 21,23-dithiaporphyirns could be potentially used as an ambipolar material for organic electronic applications.

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“…Additionally, expansion of the p-system of the porphyrin offers a means to modulate the redox and photophysical properties of the macrocycle. [3][4][5][6][7][8][9][10] This is also the case with related phthalocyanines and porphyrazines. 6,11,12 Recently, we presented an efficient synthetic protocol for stepwise elaboration of the pyrrolic faces of a porphyrin.…”

Section: Introductionmentioning

confidence: 72%