A rigid chlorin-naphthalene diimide conjugate. A possible new noncovalent electron transfer model system
Described in this paper is the synthesis and study of a rigid "coplanar" noncovalent electron-transfer model system. This putative noncovalent complex juxtaposes a novel donor (chlorin) and acceptor (naphthalene diimide) via a three-point hydrogen bonding interaction (CDCl3, Ka = 364 ± 47 M-1). It was studied by steady state fluorescence, time-resolved luminescence, and transient absorption methods. The results of the studies are consistent with (1) forward intraensemble electron transfer (ET) taking place rapidly following photoexcitation of the chlorin donor at 575 nm (kET = 7.6 × 108 s-1; ΔGcs ~ -457 mV; Φ = 0.91) and (2) back electron transfer occurring even more rapidly.
Sessler, Jonathan L.,Brown, Christopher T.,O'Connor, Don,Springs, Stacy L.,Wang, Ruizheng,Sathiosatham, Muhunthan,Hirose, Takuji
Direct measurement of photoinduced charge separation distances in donor-acceptor systems for artificial photosynthesis using OOP-ESEEM
(Graph Presented) The distance over which two photogenerated charges areseparated in electron donor-acceptor systems for artificial photosynthe sis depends on the structure of the system, while the lifetime of the charge separation and, ultimately, its ab
Carmieli, Raanan,Mi, Qixi,Ricks, Annie Butler,Giacobbe, Emilie M.,Mickley, Sarah M.,Wasielewski, Michael R.
supporting information; experimental part
p. 8372 - 8373
(2009/10/23)
Comparative PCET study of a donor-acceptor pair linked by ionized and nonionized asymmetric hydrogen-bonded interfaces
A Zn(II) amidinium porphyrin is the excited-state electron donor (D) to a naphthalene diimide acceptor (A) appended with either a carboxylate orsulfonate functionality. The two-point hydrogen bond (...[H+ ]...) formed between the amidinium and carboxylate or sulfonate functionalities establishes a proton-coupled electron transfer (PCET) pathway for charge transfer. The two D...[H+]...A assemblies differ only by the proton configuration within the hydrogen-bonding interface. Specifically, the amidinium ion transfers a proton to the carboxylate to form a nonionized amidine-carboxylic acid two-point hydrogen network, whereas the amidinium retains both protons when bound to the sulfonate functionality, forming an ionized amidinium-sulfonate two-point hydrogen bondnetwork. These two interface configurations within the dyads thus allow for a direct comparison of the PCET kinetics for the same donor and acc eptor juxtaposed by ionized and nonionized hydrogen-bonded interfaces. Analysis of the PCET kinetics ascertained from transient absorption and transient emission spectroscopy reveals that the ionized interface is more strongly impacted by the local solvent environment, thus establishing that the initial static configuration of the proton interface is a critical determinant in the kinetics of PCET.
Young, Elizabeth R.,Rosenthal, Joel,Hodgkiss, Justin M.,Nocera, Daniel G.
experimental part
p. 7678 - 7684
(2009/10/17)
NOVEL COMPOUND AND ORGANIC ELECTRONIC DEVICE USING SUCH COMPOUND
Disclosed is a novel compound suitable as an electron transporting material for organic electronic devices. Also disclosed is an organic electronic device using such a compound which has higher sensitivity and longer life than conventional organic electro
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Page/Page column 53
(2008/06/13)
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