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Study of Bridge Effects on Electroni...

Zhang, Jinyuan.

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Study of Bridge Effects on Electronic Coupling of Donor-Bridge-Acceptor Biradical Complexes.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Study of Bridge Effects on Electronic Coupling of Donor-Bridge-Acceptor Biradical Complexes./
作者:	Zhang, Jinyuan.
出版者:	Ann Arbor : ProQuest Dissertations & Theses, : 2016,
面頁冊數:	169 p.
附註:	Source: Dissertation Abstracts International, Volume: 78-08(E), Section: B.
Contained By:	Dissertation Abstracts International78-08B(E).
標題:	Physical chemistry. -
電子資源:	http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=10585487
ISBN:	9781369639599

Study of Bridge Effects on Electronic Coupling of Donor-Bridge-Acceptor Biradical Complexes.
Zhang, Jinyuan.

Study of Bridge Effects on Electronic Coupling of Donor-Bridge-Acceptor Biradical Complexes. - Ann Arbor : ProQuest Dissertations & Theses, 2016 - 169 p.

Source: Dissertation Abstracts International, Volume: 78-08(E), Section: B.

Thesis (Ph.D.)--North Carolina State University, 2016.

A series of Donor-Bridge-Acceptor (D-B-A) (D: S=1/2 ortho-semiquinonate, SQ; A: S=1/2 nitronlynitroxide, NN) biradical complexes featuring different bridges were synthesized to serve as ground state analogues of charge separated excited states as well as molecular analogs of single-molecule break junction devices. The aim is to elucidate bridge-mediated electronic structure contributions to electronic coupling.

ISBN: 9781369639599Subjects--Topical Terms:

1981412
Physical chemistry.

Study of Bridge Effects on Electronic Coupling of Donor-Bridge-Acceptor Biradical Complexes.
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245 1 0 $a Study of Bridge Effects on Electronic Coupling of Donor-Bridge-Acceptor Biradical Complexes.
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300 $a 169 p.
500 $a Source: Dissertation Abstracts International, Volume: 78-08(E), Section: B.
500 $a Adviser: David Shultz.
502 $a Thesis (Ph.D.)--North Carolina State University, 2016.
520 $a A series of Donor-Bridge-Acceptor (D-B-A) (D: S=1/2 ortho-semiquinonate, SQ; A: S=1/2 nitronlynitroxide, NN) biradical complexes featuring different bridges were synthesized to serve as ground state analogues of charge separated excited states as well as molecular analogs of single-molecule break junction devices. The aim is to elucidate bridge-mediated electronic structure contributions to electronic coupling.
520 $a The study of biradicals with sterically hindered para-phenylene bridges and an "Aviram-Ratner" (bicycle[2.2.2]octane) bridge allowed for an experimentally-determined evaluation of torsionally dependent (pi) and torsionally independent (sigma) contributions to the electronic and exchange couplings at parity of donor, acceptor and donor-acceptor distance. The torsional dependence was illustrated using a 3-dimensional, "Ramachandran-type" plot that related D-B torsion and B-A torsions to both electronic and exchange couplings.
520 $a Biradicals with asymmetric thiophene-pyridine bridges were used to study a bridge's ability to affect current rectification in a molecular electronic device. Our approach uses McConnell's electronic coupling theory and Nitzan's correlation of electronic coupling with conductance (= resistance -1). Within the framework of our model, exchange coupling parameters of the biradicals were used to estimate rectification ratios of the unsymmetric bridge. This study showed that the intra-bridge torsion angles and the unexpected symmetry of the bridge LUMO conspired to create a small rectification ratio. However, the "biradical approach" is quite effective to derive key structure-property relationships that allow insight into the choice of bridge fragments for molecular rectification.
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