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Synthesis, Oxidation and Photophysic...

Lam, Yan Choi.

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Synthesis, Oxidation and Photophysics of Perfluoroborated Tetrakis(pyrophosphito)diplatinate (II) and Density Functional Theory (DFT) Study of Electrochemical CO2 Reduction by Mn Catalysts.

Record Type:	Electronic resources : Monograph/item
Title/Author:	Synthesis, Oxidation and Photophysics of Perfluoroborated Tetrakis(pyrophosphito)diplatinate (II) and Density Functional Theory (DFT) Study of Electrochemical CO2 Reduction by Mn Catalysts./
Author:	Lam, Yan Choi.
Description:	173 p.
Notes:	Source: Dissertation Abstracts International, Volume: 76-10(E), Section: B.
Contained By:	Dissertation Abstracts International76-10B(E).
Subject:	Analytical chemistry. -
Online resource:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3704745
ISBN:	9781321773439

Synthesis, Oxidation and Photophysics of Perfluoroborated Tetrakis(pyrophosphito)diplatinate (II) and Density Functional Theory (DFT) Study of Electrochemical CO2 Reduction by Mn Catalysts.
Lam, Yan Choi.

Synthesis, Oxidation and Photophysics of Perfluoroborated Tetrakis(pyrophosphito)diplatinate (II) and Density Functional Theory (DFT) Study of Electrochemical CO2 Reduction by Mn Catalysts. - 173 p.

Source: Dissertation Abstracts International, Volume: 76-10(E), Section: B.

Thesis (Ph.D.)--California Institute of Technology, 2015.

In the first part of this thesis (Chapters I and II), the synthesis, characterization, reactivity and photophysics of per(difluoroborated) tetrakis(pyrophosphito)diplatinate(II) (Pt(POPBF2)) are discussed. Pt(POP-BF2) was obtained by reaction of [Pt2(POP) 4]4- with neat boron trifluoride diethyl etherate (BF 3&dot;Et2O). While Pt(POP-BF2) and [Pt2(POP) 4]4- have similar structures and absorption spectra, they differ in significant ways. Firstly, as discussed in Chapter I, the former is less susceptible to oxidation, as evidenced by the reversibility of its oxidation by I2. Secondly, while the first excited triplet states (T1) of both Pt(POP-BF2) and [Pt2(POP) 4]4- exhibit long lifetimes (ca. 10 mus at room temperature) and substantial zero-field splitting (40 cm-1), Pt(POP-BF 2) also has a remarkably long-lived (1.6 ns at room temperature) singlet excited state (S1), indicating slow intersystem crossing (ISC). Fluorescence lifetime and quantum yield (QY) of Pt(POP-BF2) were measured over a range of temperatures, providing insight into the slow ISC process. The remarkable spectroscopic and photophysical properties of Pt(POP-BF 2), both in solution and as a microcrystalline powder, form the theme of Chapter II.

ISBN: 9781321773439Subjects--Topical Terms:

3168300
Analytical chemistry.

Synthesis, Oxidation and Photophysics of Perfluoroborated Tetrakis(pyrophosphito)diplatinate (II) and Density Functional Theory (DFT) Study of Electrochemical CO2 Reduction by Mn Catalysts.
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020 $a 9781321773439
035 $a (MiAaPQ)AAI3704745
035 $a AAI3704745
040 $a MiAaPQ $c MiAaPQ
100 1 $a Lam, Yan Choi. $3 3192973
245 1 0 $a Synthesis, Oxidation and Photophysics of Perfluoroborated Tetrakis(pyrophosphito)diplatinate (II) and Density Functional Theory (DFT) Study of Electrochemical CO2 Reduction by Mn Catalysts.
300 $a 173 p.
500 $a Source: Dissertation Abstracts International, Volume: 76-10(E), Section: B.
500 $a Advisers: Harry B. Gray; William A. Goddard.
502 $a Thesis (Ph.D.)--California Institute of Technology, 2015.
520 $a In the first part of this thesis (Chapters I and II), the synthesis, characterization, reactivity and photophysics of per(difluoroborated) tetrakis(pyrophosphito)diplatinate(II) (Pt(POPBF2)) are discussed. Pt(POP-BF2) was obtained by reaction of [Pt2(POP) 4]4- with neat boron trifluoride diethyl etherate (BF 3&dot;Et2O). While Pt(POP-BF2) and [Pt2(POP) 4]4- have similar structures and absorption spectra, they differ in significant ways. Firstly, as discussed in Chapter I, the former is less susceptible to oxidation, as evidenced by the reversibility of its oxidation by I2. Secondly, while the first excited triplet states (T1) of both Pt(POP-BF2) and [Pt2(POP) 4]4- exhibit long lifetimes (ca. 10 mus at room temperature) and substantial zero-field splitting (40 cm-1), Pt(POP-BF 2) also has a remarkably long-lived (1.6 ns at room temperature) singlet excited state (S1), indicating slow intersystem crossing (ISC). Fluorescence lifetime and quantum yield (QY) of Pt(POP-BF2) were measured over a range of temperatures, providing insight into the slow ISC process. The remarkable spectroscopic and photophysical properties of Pt(POP-BF 2), both in solution and as a microcrystalline powder, form the theme of Chapter II.
520 $a In the second part of the thesis (Chapters III and IV), the electrochemical reduction of CO2 to CO by [(L)Mn(CO)3]- catalysts is investigated using density functional theory (DFT). As discussed in Chapter III, the turnover frequency (TOF)-limiting step is the dehydroxylation of [(bpy)Mn(CO)3(CO2H)]0/- (bpy = bipyridine) by trifluoroethanol (TFEH) to form [(bpy)Mn(CO)4]+/0. Because the dehydroxylation of [(bpy)Mn(CO)3(CO2H)] - is faster, maximum TOF (TOFmax) is achieved at potentials sufficient to completely reduce [(bpy)Mn(CO)3(CO2H)] 0 to [(bpy)Mn(CO)3(CO2H)]-. Substitution of bipyridine with bipyrimidine reduces the overpotential needed, but at the expense of TOFmax. In Chapter IV, the decoration of the bipyrimidine ligand with a pendant alcohol is discussed as a strategy to increase CO 2 reduction activity. Our calculations predict that the pendant alcohol acts in concert with an external TFEH molecule, the latter acidifying the former, resulting in a &sim; 80,000-fold improvement in the rate of TOF-limiting dehydroxylation of [(L)Mn(CO)3(CO2H)]-.
520 $a An interesting strategy for the co-upgrading of light olefins and alkanes into heavier alkanes is the subject of Appendix B. The proposed scheme involves dimerization of the light olefin, operating in tandem with transfer hydrogenation between the olefin dimer and the light alkane. The work presented therein involved a Ta olefin dimerization catalyst and a silica-supported Ir transfer hydrogenation catalyst. Olefin dimer was formed under reaction conditions; however, this did not undergo transfer hydrogenation with the light alkane. A significant challenge is that the Ta catalyst selectively produces highly branched dimers, which are unable to undergo transfer hydrogenation.
590 $a School code: 0037.
650 4 $a Analytical chemistry. $3 3168300
650 4 $a Organic chemistry. $3 523952
650 4 $a Inorganic chemistry. $3 3173556
690 $a 0486
690 $a 0490
690 $a 0488
710 2 $a California Institute of Technology. $b Chemistry. $3 2096080
773 0 $t Dissertation Abstracts International $g 76-10B(E).
790 $a 0037
791 $a Ph.D.
792 $a 2015
793 $a English
856 4 0 $u http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3704745