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

Kemisk Institut

27 Citationer (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.

Originalsprog	Engelsk
Tidsskrift	Inorganic Chemistry
Vol/bind	51
Udgave nummer	14
Sider (fra-til)	7457-7459
Antal sider	3
ISSN	0020-1669
DOI	https://doi.org/10.1021/ic301059p
Status	Udgivet - 16 jul. 2012

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10.1021/ic301059p

Citationsformater

@article{eac653f4e0c147b88a149a5f30df69f8,

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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