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Title: Work function reduction by a redox-active organometallic sandwich complex

Authors:
ORCiD logo; ; ; ;
Publication Date:
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1405194
Grant/Contract Number:
SC0001084
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Organic Electronics
Additional Journal Information:
Journal Volume: 37; Journal Issue: C; Related Information: CHORUS Timestamp: 2017-10-27 04:23:40; Journal ID: ISSN 1566-1199
Publisher:
Elsevier
Country of Publication:
Netherlands
Language:
English

Citation Formats

Hyla, Alexander S., Winget, Paul, Li, Hong, Risko, Chad, and Brédas, Jean-Luc. Work function reduction by a redox-active organometallic sandwich complex. Netherlands: N. p., 2016. Web. doi:10.1016/j.orgel.2016.06.034.
Hyla, Alexander S., Winget, Paul, Li, Hong, Risko, Chad, & Brédas, Jean-Luc. Work function reduction by a redox-active organometallic sandwich complex. Netherlands. doi:10.1016/j.orgel.2016.06.034.
Hyla, Alexander S., Winget, Paul, Li, Hong, Risko, Chad, and Brédas, Jean-Luc. 2016. "Work function reduction by a redox-active organometallic sandwich complex". Netherlands. doi:10.1016/j.orgel.2016.06.034.
@article{osti_1405194,
title = {Work function reduction by a redox-active organometallic sandwich complex},
author = {Hyla, Alexander S. and Winget, Paul and Li, Hong and Risko, Chad and Brédas, Jean-Luc},
abstractNote = {},
doi = {10.1016/j.orgel.2016.06.034},
journal = {Organic Electronics},
number = C,
volume = 37,
place = {Netherlands},
year = 2016,
month =
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1016/j.orgel.2016.06.034

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  • Treatment of Cp/sub 2/MH/sub 2/ (M = No, W) solutions with SO/sub 2/ has been found to rapidly and quantitatively give Cp/sub 2/M(S/sub 2/O/sub 3/) and water. Single-crystal X-ray studies of the Mo product at -95/sup 0/C revealed bidentate coordination of thiosulfate to molybdenum (Mo-O = 2.134 (4) A; Mo-S = 2.450 (2) A) with a dihedral angle between the Cp planes of 46.8/sup 0/ and a planar MoOS/sub 2/ ring. The thiosulfate complexes were found to react with aqueous HCl and HBr to produce SO/sub 2/, H/sub 2/O, and new metal-sulfur complexes of apparent stoichiometry (Cp/sub 2/M(S)(X))X (X =more » Cl, Br), characterized by infrared and proton NMR spectroscopy. Crystallographic data for Cp/sub 2/Mo(S/sub 2/O/sub 3/) are presented.« less
  • The reduction of a redox-active ligand is shown to drive reversible switching of a Cu(I) [2]pseudorotaxane ([2]PR{sup 2+}) into the reduced [3]pseudorotaxane ([3]PR{sup 2+}) by a bimolecular mechanism. The unreduced pseudorotaxanes [2]PR{sup 2+} and [3]PR{sup 2+} are initially self-assembled from the binucleating ligand, 3,6-bis(5-methyl-2-pyridine)-1,2,4,5-tetrazine (Me2BPTZ), and a preformed copper-macrocycle moiety (Cu-M{sup 2+}) based on 1,10-phenanthroline. X-ray crystallography revealed a syn geometry of the [3]PR{sup 2+}. The UV-vis-NIR spectra show low-energy metal-to-ligand charge-transfer transitions that red shift from 808 nm for [2]PR{sup 2+} to 1088 nm for [3]PR{sup 2+}. Quantitative analysis of the UV-vis-NIR titration shows the stepwise formation constants tomore » be K{sub 1} = 8.9 x 10{sup 8} M{sup -1} and K{sub 2} = 3.1 x 10{sup 6} M{sup -1}, indicative of negative cooperativity. The cyclic voltammetry (CV) and coulometry of Me{sub 2}BPTZ, [2]PR{sup 2+}, and [3]PR{sup 2+} shows the one-electron reductions at E{sub 1/2} = -0.96, -0.65, and -0.285 V, respectively, to be stabilized in a stepwise manner by each Cu{sup 2+} ion. CVs of [2]PR{sup 2+} show changes with scan rate consistent with an EC mechanism of supramolecular disproportionation after reduction: [2]PR{sup 0} + [2]PR{sup 2+} = [3]PR{sup 2+} + Me{sub 2}BPTZ{sup 0} (K*{sub D}, k{sub d}). UV-vis-NIR spectroelectrochemistry was used to confirm the 1:1 product stoichiometry for [3]PR{sup 2+}:Me{sub 2}BPTZ. The driving force ({Delta}G*{sub D} = -5.1 kcal mol{sup -1}) for the reaction is based on the enhanced stability of the reduced [3]PR{sup 2+} over reduced [2]PR{sup 0} by 365 mV (8.4 kcal mol{sup -1}). Digital simulations of the CVs are consistent with a bimolecular pathway (k{sub d} = 12,000 s{sup -1} M{sup -1}). Confirmation of the mechanism provides a basis to extend this new switching modality to molecular machines.« less