Multistate redox-active metalated triarylamines

Guillaume Grelaud; Marie P. Cifuentes; Torsten Schwich; Gilles Argouarch; Simon Petrie; Rob Stranger; Frédéric Paul; Mark G. Humphrey

doi:10.1002/ejic.201100747

Multistate redox-active metalated triarylamines

Guillaume Grelaud
, Marie P. Cifuentes
, Torsten Schwich
, Gilles Argouarch
, Simon Petrie
, Rob Stranger
, Frédéric Paul^*
, Mark G. Humphrey

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

42 Citations (Scopus)

Abstract

trans-[(η⁵-C₅H₅)Fe(η⁵- C₅H₄-η¹-C≡C)Ru(C≡C-4-C ₆H₄NPh₂)(dppe)₂] [4; dppe = 1,2-bis(diphenylphosphanyl)ethane] and trans,trans,trans-[{(η⁵- C₅H₅)Fe(η⁵-C₅H ₄-η¹-C≡C)Ru(dppe)₂(C≡C-4-C ₆H₄)}₃N] (7) have been synthesized from trans-[Ru(C≡C-4-C₆H₄NPh₂)Cl(dppe) ₂] (3) and trans,trans,trans-[{(dppe)₂ClRu(C≡C-4- C₆H₄)}₃N] (6), respectively, and the identities of trans-[Ru(C=CH-4-C₆H₄NPh₂)Cl(dppe) ₂][PF₆] (2, precursor to 3), 3, and 4 have been confirmed crystallographically. Chemical oxidation of 4 and 7 afforded the isolable mixed-valence species 4[PF₆] and 7[PF₆]₃. The CV of 4 reveals sequential loss of three electrons in fully reversible oxidation steps, whereas the CV of 7 shows five reversible redox waves; in contrast, oxidation of the precursor amines HC≡C-4-C₆H ₄NPh₂ and (HC≡C-4-C₆H₄) ₃N are irreversible processes. All oxidation processes afford reversible changes in the linear optical properties. Complementary time-dependent density functional theory (TD-DFT) studies suggest that the initial oxidation process for 4 and 7 is iron-centered and is followed by one (for 4) or three (for 7) ruthenium-centered oxidations. The final reversible oxidation is assigned by TD-DFT as delocalized along the metalla- ethynylarylamine moiety. The intense optical changes consequent on reversible oxidation, together with their charge-transfer character, suggest that 4 and 7 have potential as nonlinear as well as linear optical multistate switches.

Original language	English
Pages (from-to)	65-75
Number of pages	11
Journal	European Journal of Inorganic Chemistry
Issue number	1
DOIs	https://doi.org/10.1002/ejic.201100747
Publication status	Published - Jan 2012

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10.1002/ejic.201100747

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@article{15df510792c149978ca9993b44b7b440,

title = "Multistate redox-active metalated triarylamines",

abstract = "trans-[(η5-C5H5)Fe(η5- C5H4-η1-C≡C)Ru(C≡C-4-C 6H4NPh2)(dppe)2] [4; dppe = 1,2-bis(diphenylphosphanyl)ethane] and trans,trans,trans-[\{(η5- C5H5)Fe(η5-C5H 4-η1-C≡C)Ru(dppe)2(C≡C-4-C 6H4)\}3N] (7) have been synthesized from trans-[Ru(C≡C-4-C6H4NPh2)Cl(dppe) 2] (3) and trans,trans,trans-[\{(dppe)2ClRu(C≡C-4- C6H4)\}3N] (6), respectively, and the identities of trans-[Ru(C=CH-4-C6H4NPh2)Cl(dppe) 2][PF6] (2, precursor to 3), 3, and 4 have been confirmed crystallographically. Chemical oxidation of 4 and 7 afforded the isolable mixed-valence species 4[PF6] and 7[PF6]3. The CV of 4 reveals sequential loss of three electrons in fully reversible oxidation steps, whereas the CV of 7 shows five reversible redox waves; in contrast, oxidation of the precursor amines HC≡C-4-C6H 4NPh2 and (HC≡C-4-C6H4) 3N are irreversible processes. All oxidation processes afford reversible changes in the linear optical properties. Complementary time-dependent density functional theory (TD-DFT) studies suggest that the initial oxidation process for 4 and 7 is iron-centered and is followed by one (for 4) or three (for 7) ruthenium-centered oxidations. The final reversible oxidation is assigned by TD-DFT as delocalized along the metalla- ethynylarylamine moiety. The intense optical changes consequent on reversible oxidation, together with their charge-transfer character, suggest that 4 and 7 have potential as nonlinear as well as linear optical multistate switches.",

keywords = "Alkyne ligands, Electrochemistry, Iron, Metallocenes, Ruthenium, Sandwich complexes",

author = "Guillaume Grelaud and Cifuentes, \{Marie P.\} and Torsten Schwich and Gilles Argouarch and Simon Petrie and Rob Stranger and Fr{\'e}d{\'e}ric Paul and Humphrey, \{Mark G.\}",

year = "2012",

month = jan,

doi = "10.1002/ejic.201100747",

language = "English",

pages = "65--75",

journal = "European Journal of Inorganic Chemistry",

issn = "1434-1948",

publisher = "Wiley-VCH Verlag GmbH",

number = "1",

}

TY - JOUR

T1 - Multistate redox-active metalated triarylamines

AU - Grelaud, Guillaume

AU - Cifuentes, Marie P.

AU - Schwich, Torsten

AU - Argouarch, Gilles

AU - Petrie, Simon

AU - Stranger, Rob

AU - Paul, Frédéric

AU - Humphrey, Mark G.

PY - 2012/1

Y1 - 2012/1

N2 - trans-[(η5-C5H5)Fe(η5- C5H4-η1-C≡C)Ru(C≡C-4-C 6H4NPh2)(dppe)2] [4; dppe = 1,2-bis(diphenylphosphanyl)ethane] and trans,trans,trans-[{(η5- C5H5)Fe(η5-C5H 4-η1-C≡C)Ru(dppe)2(C≡C-4-C 6H4)}3N] (7) have been synthesized from trans-[Ru(C≡C-4-C6H4NPh2)Cl(dppe) 2] (3) and trans,trans,trans-[{(dppe)2ClRu(C≡C-4- C6H4)}3N] (6), respectively, and the identities of trans-[Ru(C=CH-4-C6H4NPh2)Cl(dppe) 2][PF6] (2, precursor to 3), 3, and 4 have been confirmed crystallographically. Chemical oxidation of 4 and 7 afforded the isolable mixed-valence species 4[PF6] and 7[PF6]3. The CV of 4 reveals sequential loss of three electrons in fully reversible oxidation steps, whereas the CV of 7 shows five reversible redox waves; in contrast, oxidation of the precursor amines HC≡C-4-C6H 4NPh2 and (HC≡C-4-C6H4) 3N are irreversible processes. All oxidation processes afford reversible changes in the linear optical properties. Complementary time-dependent density functional theory (TD-DFT) studies suggest that the initial oxidation process for 4 and 7 is iron-centered and is followed by one (for 4) or three (for 7) ruthenium-centered oxidations. The final reversible oxidation is assigned by TD-DFT as delocalized along the metalla- ethynylarylamine moiety. The intense optical changes consequent on reversible oxidation, together with their charge-transfer character, suggest that 4 and 7 have potential as nonlinear as well as linear optical multistate switches.

AB - trans-[(η5-C5H5)Fe(η5- C5H4-η1-C≡C)Ru(C≡C-4-C 6H4NPh2)(dppe)2] [4; dppe = 1,2-bis(diphenylphosphanyl)ethane] and trans,trans,trans-[{(η5- C5H5)Fe(η5-C5H 4-η1-C≡C)Ru(dppe)2(C≡C-4-C 6H4)}3N] (7) have been synthesized from trans-[Ru(C≡C-4-C6H4NPh2)Cl(dppe) 2] (3) and trans,trans,trans-[{(dppe)2ClRu(C≡C-4- C6H4)}3N] (6), respectively, and the identities of trans-[Ru(C=CH-4-C6H4NPh2)Cl(dppe) 2][PF6] (2, precursor to 3), 3, and 4 have been confirmed crystallographically. Chemical oxidation of 4 and 7 afforded the isolable mixed-valence species 4[PF6] and 7[PF6]3. The CV of 4 reveals sequential loss of three electrons in fully reversible oxidation steps, whereas the CV of 7 shows five reversible redox waves; in contrast, oxidation of the precursor amines HC≡C-4-C6H 4NPh2 and (HC≡C-4-C6H4) 3N are irreversible processes. All oxidation processes afford reversible changes in the linear optical properties. Complementary time-dependent density functional theory (TD-DFT) studies suggest that the initial oxidation process for 4 and 7 is iron-centered and is followed by one (for 4) or three (for 7) ruthenium-centered oxidations. The final reversible oxidation is assigned by TD-DFT as delocalized along the metalla- ethynylarylamine moiety. The intense optical changes consequent on reversible oxidation, together with their charge-transfer character, suggest that 4 and 7 have potential as nonlinear as well as linear optical multistate switches.

KW - Alkyne ligands

KW - Electrochemistry

KW - Iron

KW - Metallocenes

KW - Ruthenium

KW - Sandwich complexes

UR - https://www.scopus.com/pages/publications/84555218209

U2 - 10.1002/ejic.201100747

DO - 10.1002/ejic.201100747

M3 - Article

SN - 1434-1948

SP - 65

EP - 75

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

IS - 1

ER -

Multistate redox-active metalated triarylamines

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