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Spectroscopy, NMR, and Electrochemis...

Wang, Chenyi.

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Spectroscopy, NMR, and Electrochemistry Studies of Protonated Aminophenyl/Pyridyl Porphyrins and Their Application in Hydrogen Evolution.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Spectroscopy, NMR, and Electrochemistry Studies of Protonated Aminophenyl/Pyridyl Porphyrins and Their Application in Hydrogen Evolution./
Author:	Wang, Chenyi.
Published:	Ann Arbor : ProQuest Dissertations & Theses, : 2015,
Description:	134 p.
Notes:	Source: Dissertation Abstracts International, Volume: 76-08(E), Section: B.
Contained By:	Dissertation Abstracts International76-08B(E).
Subject:	Biochemistry. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3687879
ISBN:	9781321658392

Spectroscopy, NMR, and Electrochemistry Studies of Protonated Aminophenyl/Pyridyl Porphyrins and Their Application in Hydrogen Evolution.
Wang, Chenyi.

Spectroscopy, NMR, and Electrochemistry Studies of Protonated Aminophenyl/Pyridyl Porphyrins and Their Application in Hydrogen Evolution. - Ann Arbor : ProQuest Dissertations & Theses, 2015 - 134 p.

Source: Dissertation Abstracts International, Volume: 76-08(E), Section: B.

Thesis (Ph.D.)--Portland State University, 2015.

This item is not available from ProQuest Dissertations & Theses.

Spectrophotometric titrations for a full series of 4-aminophenyl/4-pyridyl meso-substituted porphyrins were carried out using methanesulfonic acid in DMSO to study the hyperporphyrin effect across different substitution patterns. The series included zero, one, two (cis and trans), three, and four meso(4-aminophenyl) groups, with the remaining meso substituents being 4-pyridyl groups. The peripheral pyridyl groups consistently protonate before the interior porphyrin pyrrole nitrogens, which protonate before the aminophenyl groups. Aminophenyl substituents increase the basicity of the pyrrole nitrogens and lead to distinctive hyperporphyrin spectra with a broad Soret band and a strong red absorption. The structure proposed to give rise to these spectra is the previously proposed charge-transfer interaction between the aminophenyl and the protonated pyrrole. A novel hyperporphyrin structure involving charge-transfer interactions between two peripheral substituents is also proposed in one case - the triply protonated (+3) porphyrin with three aminophenyl and one pyridyl substituents; two of the aminophenyl groups delocalize the charges on the interior nitrogens while the third aminophenyl group delocalizes with the protonated pyridyl.

ISBN: 9781321658392Subjects--Topical Terms:

518028
Biochemistry.

Spectroscopy, NMR, and Electrochemistry Studies of Protonated Aminophenyl/Pyridyl Porphyrins and Their Application in Hydrogen Evolution.
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100 1 $a Wang, Chenyi. $3 3281178
245 1 0 $a Spectroscopy, NMR, and Electrochemistry Studies of Protonated Aminophenyl/Pyridyl Porphyrins and Their Application in Hydrogen Evolution.
260 1 $a Ann Arbor : $b ProQuest Dissertations & Theses, $c 2015
300 $a 134 p.
500 $a Source: Dissertation Abstracts International, Volume: 76-08(E), Section: B.
500 $a Adviser: Carl C. Wamser.
502 $a Thesis (Ph.D.)--Portland State University, 2015.
506 $a This item is not available from ProQuest Dissertations & Theses.
520 $a Spectrophotometric titrations for a full series of 4-aminophenyl/4-pyridyl meso-substituted porphyrins were carried out using methanesulfonic acid in DMSO to study the hyperporphyrin effect across different substitution patterns. The series included zero, one, two (cis and trans), three, and four meso(4-aminophenyl) groups, with the remaining meso substituents being 4-pyridyl groups. The peripheral pyridyl groups consistently protonate before the interior porphyrin pyrrole nitrogens, which protonate before the aminophenyl groups. Aminophenyl substituents increase the basicity of the pyrrole nitrogens and lead to distinctive hyperporphyrin spectra with a broad Soret band and a strong red absorption. The structure proposed to give rise to these spectra is the previously proposed charge-transfer interaction between the aminophenyl and the protonated pyrrole. A novel hyperporphyrin structure involving charge-transfer interactions between two peripheral substituents is also proposed in one case - the triply protonated (+3) porphyrin with three aminophenyl and one pyridyl substituents; two of the aminophenyl groups delocalize the charges on the interior nitrogens while the third aminophenyl group delocalizes with the protonated pyridyl.
520 $a The NMR titrations for a full series of 4-aminophenyl/4-pyridyl meso-substituted porphyrins were also performed by methanesulfonic acid in DMSO. Zero, one, two (cis), three, and four meso(4-aminophenyl) groups, with the remaining meso substituents being 4-pyridyl groups are the primary compounds studied here. The inductive effect of the meso-substituents and the pi system of the macrocycle both determine the hyperporphyrin spectra, in which inductive effect has stronger influence on cis-A2Py2P and APy3P. TAPP and A3PyP both show slow exchanges from free base to hyperporphyrin, indicating these hyperporphyrin structures are stable. Both 1H-NMR and 2D NOESY spectra further validate the existence of the novel D-type hyperporphyrin from A3PyPH 3+3..
520 $a Electrochemical studies of these hyperporphyrins were also performed. The porphyrins involved here are zero, two (cis & trans), three, and four meso(4-aminophenyl) groups, with the remaining meso substituents being 4-pyridyl groups. The acid titrations were done in DMSO using methanesulfonic acid. Both TAPP and A3PyP can be extensively reduced with up to five distinct reduction waves. The hyperporphyrin from A3PyP, unlike that from TAPP, shows stable structures during the reduction, and A3PyPH3+3 was proposed to have the ability to reduce protons into hydrogen in a catalytic cycle.
590 $a School code: 0180.
650 4 $a Biochemistry. $3 518028
650 4 $a Physical chemistry. $3 1981412
690 $a 0487
690 $a 0494
710 2 $a Portland State University. $b Chemistry. $3 1675108
773 0 $t Dissertation Abstracts International $g 76-08B(E).
790 $a 0180
791 $a Ph.D.
792 $a 2015
793 $a English
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3687879