Dual charge-transfer in rhenium(I) thioether substituted hexaazanaphthalene complexes

Holly Van Der Salm; Michael G. Fraser; Raphael Horvath; Jack O. Turner; Gregory M. Greetham; Ian P. Clark; Michael Towrie; Nigel T. Lucas; Michael W. George; Keith C. Gordon

doi:10.1021/ic502179f

Dual charge-transfer in rhenium(I) thioether substituted hexaazanaphthalene complexes

Holly Van Der Salm, Michael G. Fraser, Raphael Horvath, Jack O. Turner, Gregory M. Greetham, Ian P. Clark, Michael Towrie, Nigel T. Lucas, Michael W. George, Keith C. Gordon

Department of Chemical and Environmental Engineering

Research output: Journal Publication › Article › peer-review

19 Citations (Scopus)

Abstract

The ligand 2,3,8,9,14,15-hexa(octyl-thioether)-5,6,11,12,17,18-hexaazatrinaphthalene (HATN-(SOct)₆) and its mono-, bi-, and trinuclear Re(CO)₃Cl complexes are reported. These are characterized by ¹H NMR spectroscopy and electrochemistry, and show broad, intense absorption across the visible wavelength region. Using time-dependent density functional theory (TD-DFT) calculations and resonance Raman spectroscopy these absorption bands are shown to be π → π, MLCT, ILCT(sulfur → HATN), or mixed MLCT/ILCT in nature. Time-resolved infrared spectroscopy is used to probe structural changes and dynamics on short time scales and supports the assignment of a mixed MLCT/ILCT state in which both sulfur groups and one metal center act as electron donors to the HATN core.

Original language	English
Pages (from-to)	13049-13060
Number of pages	12
Journal	Inorganic Chemistry
Volume	53
Issue number	24
DOIs	https://doi.org/10.1021/ic502179f
Publication status	Published - 15 Dec 2014

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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10.1021/ic502179f

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@article{e68b08399ed14b1db85fc0a2f1fbc8ec,

title = "Dual charge-transfer in rhenium(I) thioether substituted hexaazanaphthalene complexes",

abstract = "The ligand 2,3,8,9,14,15-hexa(octyl-thioether)-5,6,11,12,17,18-hexaazatrinaphthalene (HATN-(SOct)6) and its mono-, bi-, and trinuclear Re(CO)3Cl complexes are reported. These are characterized by 1H NMR spectroscopy and electrochemistry, and show broad, intense absorption across the visible wavelength region. Using time-dependent density functional theory (TD-DFT) calculations and resonance Raman spectroscopy these absorption bands are shown to be π → π, MLCT, ILCT(sulfur → HATN), or mixed MLCT/ILCT in nature. Time-resolved infrared spectroscopy is used to probe structural changes and dynamics on short time scales and supports the assignment of a mixed MLCT/ILCT state in which both sulfur groups and one metal center act as electron donors to the HATN core.",

author = "{Van Der Salm}, Holly and Fraser, {Michael G.} and Raphael Horvath and Turner, {Jack O.} and Greetham, {Gregory M.} and Clark, {Ian P.} and Michael Towrie and Lucas, {Nigel T.} and George, {Michael W.} and Gordon, {Keith C.}",

note = "Publisher Copyright: {\textcopyright} 2014 American Chemical Society.",

year = "2014",

month = dec,

day = "15",

doi = "10.1021/ic502179f",

language = "English",

volume = "53",

pages = "13049--13060",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Dual charge-transfer in rhenium(I) thioether substituted hexaazanaphthalene complexes

AU - Van Der Salm, Holly

AU - Fraser, Michael G.

AU - Horvath, Raphael

AU - Turner, Jack O.

AU - Greetham, Gregory M.

AU - Clark, Ian P.

AU - Towrie, Michael

AU - Lucas, Nigel T.

AU - George, Michael W.

AU - Gordon, Keith C.

PY - 2014/12/15

Y1 - 2014/12/15

N2 - The ligand 2,3,8,9,14,15-hexa(octyl-thioether)-5,6,11,12,17,18-hexaazatrinaphthalene (HATN-(SOct)6) and its mono-, bi-, and trinuclear Re(CO)3Cl complexes are reported. These are characterized by 1H NMR spectroscopy and electrochemistry, and show broad, intense absorption across the visible wavelength region. Using time-dependent density functional theory (TD-DFT) calculations and resonance Raman spectroscopy these absorption bands are shown to be π → π, MLCT, ILCT(sulfur → HATN), or mixed MLCT/ILCT in nature. Time-resolved infrared spectroscopy is used to probe structural changes and dynamics on short time scales and supports the assignment of a mixed MLCT/ILCT state in which both sulfur groups and one metal center act as electron donors to the HATN core.

AB - The ligand 2,3,8,9,14,15-hexa(octyl-thioether)-5,6,11,12,17,18-hexaazatrinaphthalene (HATN-(SOct)6) and its mono-, bi-, and trinuclear Re(CO)3Cl complexes are reported. These are characterized by 1H NMR spectroscopy and electrochemistry, and show broad, intense absorption across the visible wavelength region. Using time-dependent density functional theory (TD-DFT) calculations and resonance Raman spectroscopy these absorption bands are shown to be π → π, MLCT, ILCT(sulfur → HATN), or mixed MLCT/ILCT in nature. Time-resolved infrared spectroscopy is used to probe structural changes and dynamics on short time scales and supports the assignment of a mixed MLCT/ILCT state in which both sulfur groups and one metal center act as electron donors to the HATN core.

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U2 - 10.1021/ic502179f

DO - 10.1021/ic502179f

M3 - Article

AN - SCOPUS:84920153230

SN - 0020-1669

VL - 53

SP - 13049

EP - 13060

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 24

ER -

Dual charge-transfer in rhenium(I) thioether substituted hexaazanaphthalene complexes

Abstract

ASJC Scopus subject areas

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