skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Oxidatively stable ferrocenyl-π-bridge-titanocene D–π-A complexes: an electrochemical and spectroscopic investigation of the mixed-valent states

Abstract

Coordination of Cu Iinto RCp 2Ti(C 2Fc) 2compounds results in well-separated Fe III/IIcouples and mixed-valent states with distinct spectroscopic signatures.

Authors:
ORCiD logo [1];  [1];  [2]; ORCiD logo [1]; ORCiD logo [3];  [1];  [2]; ORCiD logo [1]
  1. Department of Chemistry; Furman University; Greenville; USA
  2. Department of Chemistry; The University of North Carolina at Chapel Hill; Chapel Hill; USA
  3. Department of Chemistry; Clemson University; Clemson; USA
Publication Date:
Research Org.:
Univ. of North Carolina, Chapel Hill, NC (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1540031
DOE Contract Number:  
SC0001011; SC0013461
Resource Type:
Journal Article
Journal Name:
Dalton Transactions
Additional Journal Information:
Journal Volume: 47; Journal Issue: 32; Journal ID: ISSN 1477-9226
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
Chemistry

Citation Formats

Pienkos, Jared A., Webster, Alexander B., Piechota, Eric J., Agakidou, A. Danai, McMillen, Colin D., Pritchett, David Y., Meyer, Gerald J., and Wagenknecht, Paul S. Oxidatively stable ferrocenyl-π-bridge-titanocene D–π-A complexes: an electrochemical and spectroscopic investigation of the mixed-valent states. United States: N. p., 2018. Web. doi:10.1039/c8dt01853g.
Pienkos, Jared A., Webster, Alexander B., Piechota, Eric J., Agakidou, A. Danai, McMillen, Colin D., Pritchett, David Y., Meyer, Gerald J., & Wagenknecht, Paul S. Oxidatively stable ferrocenyl-π-bridge-titanocene D–π-A complexes: an electrochemical and spectroscopic investigation of the mixed-valent states. United States. doi:10.1039/c8dt01853g.
Pienkos, Jared A., Webster, Alexander B., Piechota, Eric J., Agakidou, A. Danai, McMillen, Colin D., Pritchett, David Y., Meyer, Gerald J., and Wagenknecht, Paul S. Mon . "Oxidatively stable ferrocenyl-π-bridge-titanocene D–π-A complexes: an electrochemical and spectroscopic investigation of the mixed-valent states". United States. doi:10.1039/c8dt01853g.
@article{osti_1540031,
title = {Oxidatively stable ferrocenyl-π-bridge-titanocene D–π-A complexes: an electrochemical and spectroscopic investigation of the mixed-valent states},
author = {Pienkos, Jared A. and Webster, Alexander B. and Piechota, Eric J. and Agakidou, A. Danai and McMillen, Colin D. and Pritchett, David Y. and Meyer, Gerald J. and Wagenknecht, Paul S.},
abstractNote = {Coordination of CuIintoRCp2Ti(C2Fc)2compounds results in well-separated FeIII/IIcouples and mixed-valent states with distinct spectroscopic signatures.},
doi = {10.1039/c8dt01853g},
journal = {Dalton Transactions},
issn = {1477-9226},
number = 32,
volume = 47,
place = {United States},
year = {2018},
month = {1}
}

Works referenced in this record:

D-π-A Conjugated Molecules for Optoelectronic Applications
journal, March 2015

  • Kim, Tae-Dong; Lee, Kwang-Sup
  • Macromolecular Rapid Communications, Vol. 36, Issue 11
  • DOI: 10.1002/marc.201400749

The renaissance of dye-sensitized solar cells
journal, February 2012

  • Hardin, Brian E.; Snaith, Henry J.; McGehee, Michael D.
  • Nature Photonics, Vol. 6, Issue 3
  • DOI: 10.1038/nphoton.2012.22

Metal-Free Organic Dyes for Dye-Sensitized Solar Cells: From Structure: Property Relationships to Design Rules
journal, March 2009

  • Mishra, Amaresh; Fischer, Markus K. R.; Bäuerle, Peter
  • Angewandte Chemie International Edition, Vol. 48, Issue 14
  • DOI: 10.1002/anie.200804709

Molecular wires – impact of π-conjugation and implementation of molecular bottlenecks
journal, January 2015

  • Schubert, C.; Margraf, J. T.; Clark, T.
  • Chemical Society Reviews, Vol. 44, Issue 4
  • DOI: 10.1039/C4CS00262H

Charge Separation in a Novel Artificial Photosynthetic Reaction Center Lives 380 ms
journal, July 2001

  • Imahori, Hiroshi; Guldi, Dirk M.; Tamaki, Koichi
  • Journal of the American Chemical Society, Vol. 123, Issue 27
  • DOI: 10.1021/ja004123v

Ferrocene chromophores continue to inspire. Fine-tuning and switching of the second-order nonlinear optical response
journal, July 2017


Synthesis and structure of (cis)-[1-ferrocenyl-2-(4-nitrophenyl)ethylene], an organotransition metal compound with a large second-order optical nonlinearity
journal, November 1987

  • Green, Malcolm L. H.; Marder, Seth R.; Thompson, Mark E.
  • Nature, Vol. 330, Issue 6146
  • DOI: 10.1038/330360a0

An investigation of the role increasing π-conjugation has on the efficiency of dye-sensitized solar cells fabricated from ferrocene-based dyes
journal, January 2016

  • Cariello, Michele; Ahn, Sungwoo; Park, Kwang-Won
  • RSC Advances, Vol. 6, Issue 11
  • DOI: 10.1039/C5RA21565J

Ferrocenyl chalcones with phenolic and pyridyl anchors as potential sensitizers in dye-sensitized solar cells
journal, January 2016

  • Chauhan, Ratna; Yadav, Reena; Singh, Ashish Kumar
  • RSC Advances, Vol. 6, Issue 100
  • DOI: 10.1039/C6RA23034B

(D–π–A) 2 –π–D–A type ferrocenyl bisthiazole linked triphenylamine based molecular systems for DSSC: synthesis, experimental and theoretical performance studies
journal, January 2017

  • Maragani, Ramesh; Misra, Rajneesh; Roy, M. S.
  • Physical Chemistry Chemical Physics, Vol. 19, Issue 13
  • DOI: 10.1039/C7CP00612H

Application of π-Extended Ferrocene with Varied Anchoring Groups as Photosensitizers in TiO2-Based Dye-Sensitized Solar Cells (DSSCs)
journal, May 2011

  • Chauhan, Ratna; Trivedi, Manoj; Bahadur, Lal
  • Chemistry - An Asian Journal, Vol. 6, Issue 6
  • DOI: 10.1002/asia.201000845

Dye-Sensitized Solar Cells with Biferrocenyl Antennae Having Quinoxaline Spacers: DSSCs with Biferrocenyl Antennae having Quinoxaline Spacers
journal, June 2015

  • Chauhan, Ratna; Shahid, Mohammad; Trivedi, Manoj
  • European Journal of Inorganic Chemistry, Vol. 2015, Issue 22
  • DOI: 10.1002/ejic.201500488

Ferrocenyl benzimidazole with carboxylic and nitro anchors as potential sensitizers in dye-sensitized solar cells
journal, January 2017

  • Yadav, Reena; Singh, Amita; Kociok-Köhn, Gabriele
  • New J. Chem., Vol. 41, Issue 15
  • DOI: 10.1039/C7NJ01464C

Complexes with Tunable Intramolecular Ferrocene to Ti IV Electronic Transitions: Models for Solid State Fe II to Ti IV Charge Transfer
journal, February 2016


Synthesis and characterization of some pyridinium N-phenoxide betaine dyes for second-harmonic generation
journal, January 1991

  • Paley, M. Steven; Harris, J. Milton
  • The Journal of Organic Chemistry, Vol. 56, Issue 2
  • DOI: 10.1021/jo00002a017

Preparation, Characterization, Molecular and Electronic Structures, TDDFT, and TDDFT/PCM Study of the Solvatochromism in Cyanovinylferrocenes
journal, November 2007

  • Nemykin, Victor N.; Makarova, Elena A.; Grosland, Jeffrey O.
  • Inorganic Chemistry, Vol. 46, Issue 23
  • DOI: 10.1021/ic700558v

Titanocene as a New Acceptor (A) for Arylamine Donors (D) in D−π–A Chromophores
journal, July 2016


Heterocyclisation of ferrocenyl- and benzenetricarbonyl chromium-cyclopentadienes with o-quinone. Evidence for a SET route
journal, January 2004


Synthesis of a Ferrocenyl-Capped Ruthenium(II) Bis(acetylide) Complex:  A Model for Organometallic Molecular Wires
journal, April 1997

  • Jones, Nathan D.; Wolf, Michael O.; Giaquinta, D. M.
  • Organometallics, Vol. 16, Issue 7
  • DOI: 10.1021/om960849h

Effect of Ancillary Ligands on Ru(II) on Electronic Delocalization in Ruthenium(II) Bisferrocenylacetylide Complexes
journal, March 1998

  • Zhu, Yongbao; Clot, Olivier; Wolf, Michael O.
  • Journal of the American Chemical Society, Vol. 120, Issue 8
  • DOI: 10.1021/ja9732486

Electron transfer in trans-[Pt(PPh3)2(-CCFc)2] and related compounds
journal, October 1994


Photoactive Chromium(III)-Cyclam Complexes with Axially Bound geminal -Diethynylethenes
journal, November 2012

  • Forrest, William P.; Cao, Zhi; Hambrick, H. Rhodes
  • European Journal of Inorganic Chemistry, Vol. 2012, Issue 34
  • DOI: 10.1002/ejic.201201235

C 2 -Bridged Titanocene−Ferrocenyl Complexes:  Synthesis, Reaction Chemistry, and Electrochemical Behavior
journal, January 1998

  • Back, Stephan; Pritzkow, Hans; Lang, Heinrich
  • Organometallics, Vol. 17, Issue 1
  • DOI: 10.1021/om9701231

A trans -bidentate bis-pyridinyl ligand with a transition metal hinge
journal, January 2017

  • Vieira, Noah C.; Pienkos, Jared A.; McMillen, Colin D.
  • Dalton Transactions, Vol. 46, Issue 44
  • DOI: 10.1039/C7DT03252H

A Practical Beginner’s Guide to Cyclic Voltammetry
journal, November 2017

  • Elgrishi, Noémie; Rountree, Kelley J.; McCarthy, Brian D.
  • Journal of Chemical Education, Vol. 95, Issue 2
  • DOI: 10.1021/acs.jchemed.7b00361

Perturbation of the Charge Density between Two Bridged Mo 2 Centers: The Remote Substituent Effects
journal, August 2014

  • Cheng, Tao; Meng, Miao; Lei, Hao
  • Inorganic Chemistry, Vol. 53, Issue 17
  • DOI: 10.1021/ic501313q

New Fe(III)(cyclam) Complexes Bearing Axially Bound geminal -Diethynylethenes
journal, August 2013

  • Cao, Zhi; Fanwick, Phillip E.; Forrest, William P.
  • Organometallics, Vol. 32, Issue 16
  • DOI: 10.1021/om400683d

Unsymmetric Mononuclear and Bridged Dinuclear Co III (cyclam) Acetylides
journal, February 2014

  • Cook, Timothy D.; Fanwick, Phillip E.; Ren, Tong
  • Organometallics, Vol. 33, Issue 18
  • DOI: 10.1021/om401231j

A Synthetic Approach to Cross-Conjugated Organometallic Complexes Based on geminal -Diethynylethene and Co III (cyclam)
journal, October 2016


Stepwise Synthesis of Bis-Alkynyl Co III (cyclam) Complexes under Ambient Conditions
journal, June 2016


Co III (cyclam) Oligoynyls: Monomeric Oligoynyl Complexes and Dimeric Complexes with an Oligoyn-diyl Bridge
journal, April 2016


trans -[Fe(cyclam)(C 2 R) 2 ] + : A New Family of Iron(III) Bis-Alkynyl Compounds
journal, August 2012

  • Cao, Zhi; Forrest, William P.; Gao, Yang
  • Organometallics, Vol. 31, Issue 17
  • DOI: 10.1021/om300515r

The influence of an ethynyl spacer on the electronic properties in 2,5-ferrocenyl-substituted heterocycles
journal, January 2015


Manipulating the Electrolyte Medium to Favor Either One-Electron or Two-Electron Oxidation Pathways for (Fulvalendiyl)dirhodium Complexes
journal, March 2006

  • Nafady, Ayman; Chin, Teen T.; Geiger, William E.
  • Organometallics, Vol. 25, Issue 7
  • DOI: 10.1021/om051101e

Use of Medium Effects to Tune the Δ E 1/2 Values of Bimetallic and Oligometallic Compounds
journal, June 2002

  • Barrière, Frédéric; Camire, Nicole; Geiger, William E.
  • Journal of the American Chemical Society, Vol. 124, Issue 25
  • DOI: 10.1021/ja020309d

Ferrocenyl-Terminated Redox Stars: Synthesis and Electrostatic Effects in Mixed-Valence Stabilization
journal, January 2011

  • Diallo, Abdou K.; Absalon, Christelle; Ruiz, Jaime
  • Journal of the American Chemical Society, Vol. 133, Issue 3
  • DOI: 10.1021/ja109380u

Tetrapyrrole Derivatives Substituted with Ferrocenylethynyl Moieties. Synthesis and Electrochemical Studies
journal, March 2001

  • Poon, Ka-Wo; Liu, Wei; Chan, Pui-Kwan
  • The Journal of Organic Chemistry, Vol. 66, Issue 5
  • DOI: 10.1021/jo0004308

A Simple and Efficient Synthesis of Di-, Tri-, and Tetraferrocenylarenes
journal, January 1997

  • Iyoda, Masahiko; Kondo, Terumasa; Okabe, Toshitaka
  • Chemistry Letters, Vol. 26, Issue 1
  • DOI: 10.1246/cl.1997.35

(Multi)ferrocenyl Five-Membered Heterocycles: Excellent Connecting Units for Electron Transfer Studies
journal, August 2013

  • Hildebrandt, Alexander; Lang, Heinrich
  • Organometallics, Vol. 32, Issue 20
  • DOI: 10.1021/om400453m

Electron Transfer Studies on Ferrocenylthiophenes: Synthesis, Properties, and Electrochemistry
journal, August 2012

  • Speck, J. Matthäus; Claus, Ron; Hildebrandt, Alexander
  • Organometallics, Vol. 31, Issue 17
  • DOI: 10.1021/om3006036

Optical Intramolecular Electron Transfer in Opposite Directions through the Same Bridge That Follows Different Pathways
journal, May 2018

  • Piechota, Eric J.; Troian-Gautier, Ludovic; Sampaio, Renato N.
  • Journal of the American Chemical Society, Vol. 140, Issue 23
  • DOI: 10.1021/jacs.8b02715

1-Cyano-1′-ethynyl-ferrocene: Synthesis and reaction chemistry
journal, June 2015


Synthesis, Structure, and Redox Chemistry of Ethenyl and Ethynyl Ferrocene Polyaromatic Dyads
journal, April 2005

  • Cuffe, Laurence; Hudson, Richard D. A.; Gallagher, John F.
  • Organometallics, Vol. 24, Issue 9
  • DOI: 10.1021/om0492653

Quantum-chemical insights into mixed-valence systems: within and beyond the Robin–Day scheme
journal, January 2014


Asymmetric Mixed-Valence Complexes that Consist of Cyclometalated Ruthenium and Ferrocene: Synthesis, Characterization, and Electronic-Coupling Studies
journal, October 2012

  • Wu, Si-Hai; Shen, Jun-Jian; Yao, Jiannian
  • Chemistry - An Asian Journal, Vol. 8, Issue 1
  • DOI: 10.1002/asia.201200900

Conformation-Determined Through-Bond versus Through-Space Electronic Communication in Mixed-Valence Systems with a Cross-Conjugated Urea Bridge
journal, November 2014

  • Gong, Zhong-Liang; Zhong, Yu-Wu; Yao, Jiannian
  • Chemistry - A European Journal, Vol. 21, Issue 4
  • DOI: 10.1002/chem.201405332

Metal—lingad and metal—metal coupling elements
journal, August 1994

  • Creutz, Carol; Newton, Marshall D.; Sutin, Norman
  • Journal of Photochemistry and Photobiology A: Chemistry, Vol. 82, Issue 1-3
  • DOI: 10.1016/1010-6030(94)02013-2

Photoinduced electron transfer across molecular bridges: electron- and hole-transfer superexchange pathways
journal, January 2014

  • Natali, Mirco; Campagna, Sebastiano; Scandola, Franco
  • Chem. Soc. Rev., Vol. 43, Issue 12
  • DOI: 10.1039/C3CS60463B