Enhancing the stability of trinickel molecular wires and switches: Ni36+/Ni37+

John F. Berry; F. Albert Cotton; Tongbu Lu; Carlos A. Murillo; Xiaoping Wang

doi:10.1021/ic0341486

Enhancing the stability of trinickel molecular wires and switches: Ni₃⁶⁺/Ni₃⁷⁺

John F. Berry, F. Albert Cotton, Tongbu Lu, Carlos A. Murillo, Xiaoping Wang

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Abstract

This paper describes in detail four new compounds that contain extended metal atom chains (EMACs) of three nickel atoms wrapped by either di(2-pyridyl)amide (dpa) or the new homologous ligand with an ethyl group at the para position of each pyridyl group, depa, and compares them to the precursor Ni₃(dpa)₄Cl₂ (1) and the oxidized and rather unstable Ni₃(dpa)₄(PF₆)₃ (2). The new molecules are Ni₃(depa)₄Cl₂ (3), Ni₃(depa)₄(PF₆)₃ (4), [Ni₃(dpa)₄(CH₃CN)₂] (PF₆)₂ (5), and [i₃(depa)₄(CH₃CN)₂] (PF₆)₂ (6). These compounds are fully described as to preparation, elemental composition, structure, infrared spectra, ¹H NMR spectra (where possible), electrochemistry, magnetic susceptibility, and an EPR spectrum for 4. The effects of (a) introducing the ethyl substituents on the ligands, (b) replacing axial anions by neutral axial ligands, and (c) oxidizing the Ni₃ chains are reported and discussed. The point of major interest is how oxidation profoundly alters the electronic structure of the EMAC.

Original language	English
Pages (from-to)	3595-3601
Number of pages	7
Journal	Inorganic Chemistry
Volume	42
Issue number	11
DOIs	https://doi.org/10.1021/ic0341486
State	Published - Jun 2 2003
Externally published	Yes

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title = "Enhancing the stability of trinickel molecular wires and switches: Ni36+/Ni37+",

abstract = "This paper describes in detail four new compounds that contain extended metal atom chains (EMACs) of three nickel atoms wrapped by either di(2-pyridyl)amide (dpa) or the new homologous ligand with an ethyl group at the para position of each pyridyl group, depa, and compares them to the precursor Ni3(dpa)4Cl2 (1) and the oxidized and rather unstable Ni3(dpa)4(PF6)3 (2). The new molecules are Ni3(depa)4Cl2 (3), Ni3(depa)4(PF6)3 (4), [Ni3(dpa)4(CH3CN)2] (PF6)2 (5), and [i3(depa)4(CH3CN)2] (PF6)2 (6). These compounds are fully described as to preparation, elemental composition, structure, infrared spectra, 1H NMR spectra (where possible), electrochemistry, magnetic susceptibility, and an EPR spectrum for 4. The effects of (a) introducing the ethyl substituents on the ligands, (b) replacing axial anions by neutral axial ligands, and (c) oxidizing the Ni3 chains are reported and discussed. The point of major interest is how oxidation profoundly alters the electronic structure of the EMAC.",

author = "Berry, {John F.} and Cotton, {F. Albert} and Tongbu Lu and Murillo, {Carlos A.} and Xiaoping Wang",

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AU - Wang, Xiaoping

PY - 2003/6/2

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AB - This paper describes in detail four new compounds that contain extended metal atom chains (EMACs) of three nickel atoms wrapped by either di(2-pyridyl)amide (dpa) or the new homologous ligand with an ethyl group at the para position of each pyridyl group, depa, and compares them to the precursor Ni3(dpa)4Cl2 (1) and the oxidized and rather unstable Ni3(dpa)4(PF6)3 (2). The new molecules are Ni3(depa)4Cl2 (3), Ni3(depa)4(PF6)3 (4), [Ni3(dpa)4(CH3CN)2] (PF6)2 (5), and [i3(depa)4(CH3CN)2] (PF6)2 (6). These compounds are fully described as to preparation, elemental composition, structure, infrared spectra, 1H NMR spectra (where possible), electrochemistry, magnetic susceptibility, and an EPR spectrum for 4. The effects of (a) introducing the ethyl substituents on the ligands, (b) replacing axial anions by neutral axial ligands, and (c) oxidizing the Ni3 chains are reported and discussed. The point of major interest is how oxidation profoundly alters the electronic structure of the EMAC.

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Enhancing the stability of trinickel molecular wires and switches: Ni₃⁶⁺/Ni₃⁷⁺

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