Synthesis and characterization of a neutral titanium tris(iminosemiquinone) complex featuring redox-active ligands

Kensha Marie Clark; Jesper Bendix; Alan F. Heyduk; Joseph W. Ziller

doi:10.1021/ic301059p

Synthesis and characterization of a neutral titanium tris(iminosemiquinone) complex featuring redox-active ligands

Kensha Marie Clark, Jesper Bendix, Alan F. Heyduk, Joseph W. Ziller

Department of Chemistry

27 Citations (Scopus)

Abstract

The neutral tris(semiquinonate) complex [Ti(dmp-BIAN^isq) ₃] [dmp-BIAN^isq = N,N'-bis(3,5-dimethylphenylimino) acenaphthenesemiquinonate] was structurally, spectroscopically, and electrochemically characterized. Solid-state magnetism experiments reveal field-quenchable, enhanced temperature-independent paramagnetism (TIP). Density functional theory calculations employing the experimental geometry predicts a strong antiferromagnetic coupling, leading to an S = 0 ground state, but they also hint at spin frustration and concomitant close-lying, excited states, which cause the observed large TIP by admixture into the ground state. The dmp-BIAN^isq ligand, which facilitates intramolecular electron transfer, was shown to undergo four quasi-reversible redox processes, demonstrating the ability of the ligand to act as an electron reservoir in complexes of early metals.

Original language	English
Journal	Inorganic Chemistry
Volume	51
Issue number	14
Pages (from-to)	7457-7459
Number of pages	3
ISSN	0020-1669
DOIs	https://doi.org/10.1021/ic301059p
Publication status	Published - 16 Jul 2012

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title = "Synthesis and characterization of a neutral titanium tris(iminosemiquinone) complex featuring redox-active ligands",

abstract = "The neutral tris(semiquinonate) complex [Ti(dmp-BIANisq) 3] [dmp-BIANisq = N,N'-bis(3,5-dimethylphenylimino) acenaphthenesemiquinonate] was structurally, spectroscopically, and electrochemically characterized. Solid-state magnetism experiments reveal field-quenchable, enhanced temperature-independent paramagnetism (TIP). Density functional theory calculations employing the experimental geometry predicts a strong antiferromagnetic coupling, leading to an S = 0 ground state, but they also hint at spin frustration and concomitant close-lying, excited states, which cause the observed large TIP by admixture into the ground state. The dmp-BIANisq ligand, which facilitates intramolecular electron transfer, was shown to undergo four quasi-reversible redox processes, demonstrating the ability of the ligand to act as an electron reservoir in complexes of early metals.",

author = "Clark, {Kensha Marie} and Jesper Bendix and Heyduk, {Alan F.} and Ziller, {Joseph W.}",

year = "2012",

month = jul,

day = "16",

doi = "10.1021/ic301059p",

language = "English",

volume = "51",

pages = "7457--7459",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Synthesis and characterization of a neutral titanium tris(iminosemiquinone) complex featuring redox-active ligands

AU - Clark, Kensha Marie

AU - Bendix, Jesper

AU - Heyduk, Alan F.

AU - Ziller, Joseph W.

PY - 2012/7/16

Y1 - 2012/7/16

N2 - The neutral tris(semiquinonate) complex [Ti(dmp-BIANisq) 3] [dmp-BIANisq = N,N'-bis(3,5-dimethylphenylimino) acenaphthenesemiquinonate] was structurally, spectroscopically, and electrochemically characterized. Solid-state magnetism experiments reveal field-quenchable, enhanced temperature-independent paramagnetism (TIP). Density functional theory calculations employing the experimental geometry predicts a strong antiferromagnetic coupling, leading to an S = 0 ground state, but they also hint at spin frustration and concomitant close-lying, excited states, which cause the observed large TIP by admixture into the ground state. The dmp-BIANisq ligand, which facilitates intramolecular electron transfer, was shown to undergo four quasi-reversible redox processes, demonstrating the ability of the ligand to act as an electron reservoir in complexes of early metals.

AB - The neutral tris(semiquinonate) complex [Ti(dmp-BIANisq) 3] [dmp-BIANisq = N,N'-bis(3,5-dimethylphenylimino) acenaphthenesemiquinonate] was structurally, spectroscopically, and electrochemically characterized. Solid-state magnetism experiments reveal field-quenchable, enhanced temperature-independent paramagnetism (TIP). Density functional theory calculations employing the experimental geometry predicts a strong antiferromagnetic coupling, leading to an S = 0 ground state, but they also hint at spin frustration and concomitant close-lying, excited states, which cause the observed large TIP by admixture into the ground state. The dmp-BIANisq ligand, which facilitates intramolecular electron transfer, was shown to undergo four quasi-reversible redox processes, demonstrating the ability of the ligand to act as an electron reservoir in complexes of early metals.

U2 - 10.1021/ic301059p

DO - 10.1021/ic301059p

M3 - Journal article

C2 - 22747661

SN - 0020-1669

VL - 51

SP - 7457

EP - 7459

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 14

ER -

Synthesis and characterization of a neutral titanium tris(iminosemiquinone) complex featuring redox-active ligands

Abstract

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