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",

number = "24",

}

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.

UR - https://www.scopus.com/pages/publications/84920153230

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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