Long-Lived Charge Transfer Excited States in HBC-Polypyridyl Complex Hybrids

Anastasia B.S. Elliott; Raphael Horvath; Xue Zhong Sun; Michael G. Gardiner; Klaus Müllen; Nigel T. Lucas; Michael W. George; Keith C. Gordon

doi:10.1021/acs.inorgchem.5b02602

Long-Lived Charge Transfer Excited States in HBC-Polypyridyl Complex Hybrids

Anastasia B.S. Elliott, Raphael Horvath, Xue Zhong Sun, Michael G. Gardiner, Klaus Müllen, Nigel T. Lucas, Michael W. George, Keith C. Gordon

Department of Chemical and Environmental Engineering

Research output: Journal Publication › Article › peer-review

20 Citations (Scopus)

Abstract

The synthesis of two bipyridine-hexa-peri-hexabenzocoronene (bpy-HBC) ligands functionalized with either ^tBu or C₁₂H₂₅ and their Re(I) tricarbonyl chloride complexes are reported and their electronic properties investigated using spectroscopic and computational methods. The metal complexes show unusual properties, and we observed the formation of a long-lived excited state using time-resolved infrared spectroscopy. Depending on the solvent, this appears to be of the form Rebpy^•-HBC^•+ or a bpy-centered π,π∗ state. TD-DFT calculations support the donor-acceptor charge transfer character of these systems, in which HBC is the donor and bpy is the acceptor. The ground state optical properties are dominated by the HBC chromophore with additional distinct transitions of the complexes, one associated with MLCT 450 nm (ϵ > 17"000 L mol^-1 cm^-1) and another with a HBC/metal to bpy charge transfer, termed the MLLCT band (373 nm, ϵ = 66"000 L mol^-1 cm^-1). These assignments are also supported by resonance Raman spectroscopy.

Original language	English
Pages (from-to)	4710-4719
Number of pages	10
Journal	Inorganic Chemistry
Volume	55
Issue number	10
DOIs	https://doi.org/10.1021/acs.inorgchem.5b02602
Publication status	Published - 16 May 2016

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{5b59721f32db4faab690deb34ab20218,

title = "Long-Lived Charge Transfer Excited States in HBC-Polypyridyl Complex Hybrids",

abstract = "The synthesis of two bipyridine-hexa-peri-hexabenzocoronene (bpy-HBC) ligands functionalized with either tBu or C12H25 and their Re(I) tricarbonyl chloride complexes are reported and their electronic properties investigated using spectroscopic and computational methods. The metal complexes show unusual properties, and we observed the formation of a long-lived excited state using time-resolved infrared spectroscopy. Depending on the solvent, this appears to be of the form Rebpy•-HBC•+ or a bpy-centered π,π∗ state. TD-DFT calculations support the donor-acceptor charge transfer character of these systems, in which HBC is the donor and bpy is the acceptor. The ground state optical properties are dominated by the HBC chromophore with additional distinct transitions of the complexes, one associated with MLCT 450 nm (ϵ > 17{"}000 L mol-1 cm-1) and another with a HBC/metal to bpy charge transfer, termed the MLLCT band (373 nm, ϵ = 66{"}000 L mol-1 cm-1). These assignments are also supported by resonance Raman spectroscopy.",

author = "Elliott, {Anastasia B.S.} and Raphael Horvath and Sun, {Xue Zhong} and Gardiner, {Michael G.} and Klaus M{\"u}llen and Lucas, {Nigel T.} and George, {Michael W.} and Gordon, {Keith C.}",

note = "Publisher Copyright: {\textcopyright} 2016 American Chemical Society.",

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doi = "10.1021/acs.inorgchem.5b02602",

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AU - Elliott, Anastasia B.S.

AU - Horvath, Raphael

AU - Sun, Xue Zhong

AU - Gardiner, Michael G.

AU - Müllen, Klaus

AU - Lucas, Nigel T.

AU - George, Michael W.

AU - Gordon, Keith C.

PY - 2016/5/16

Y1 - 2016/5/16

N2 - The synthesis of two bipyridine-hexa-peri-hexabenzocoronene (bpy-HBC) ligands functionalized with either tBu or C12H25 and their Re(I) tricarbonyl chloride complexes are reported and their electronic properties investigated using spectroscopic and computational methods. The metal complexes show unusual properties, and we observed the formation of a long-lived excited state using time-resolved infrared spectroscopy. Depending on the solvent, this appears to be of the form Rebpy•-HBC•+ or a bpy-centered π,π∗ state. TD-DFT calculations support the donor-acceptor charge transfer character of these systems, in which HBC is the donor and bpy is the acceptor. The ground state optical properties are dominated by the HBC chromophore with additional distinct transitions of the complexes, one associated with MLCT 450 nm (ϵ > 17"000 L mol-1 cm-1) and another with a HBC/metal to bpy charge transfer, termed the MLLCT band (373 nm, ϵ = 66"000 L mol-1 cm-1). These assignments are also supported by resonance Raman spectroscopy.

AB - The synthesis of two bipyridine-hexa-peri-hexabenzocoronene (bpy-HBC) ligands functionalized with either tBu or C12H25 and their Re(I) tricarbonyl chloride complexes are reported and their electronic properties investigated using spectroscopic and computational methods. The metal complexes show unusual properties, and we observed the formation of a long-lived excited state using time-resolved infrared spectroscopy. Depending on the solvent, this appears to be of the form Rebpy•-HBC•+ or a bpy-centered π,π∗ state. TD-DFT calculations support the donor-acceptor charge transfer character of these systems, in which HBC is the donor and bpy is the acceptor. The ground state optical properties are dominated by the HBC chromophore with additional distinct transitions of the complexes, one associated with MLCT 450 nm (ϵ > 17"000 L mol-1 cm-1) and another with a HBC/metal to bpy charge transfer, termed the MLLCT band (373 nm, ϵ = 66"000 L mol-1 cm-1). These assignments are also supported by resonance Raman spectroscopy.

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Long-Lived Charge Transfer Excited States in HBC-Polypyridyl Complex Hybrids

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