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Alkyl chain functionalised, cyclometalated platinum(II) complexes: syntheses, luminescence properties and X-ray crystal structure

Alkyl chain functionalised, cyclometalated platinum(II) complexes: syntheses, luminescence properties and X-ray crystal structure
Alkyl chain functionalised, cyclometalated platinum(II) complexes: syntheses, luminescence properties and X-ray crystal structure
The synthesis and characterisation of nine new monometallic heteroleptic platinum complexes [PtCl(L1–3)(DMSO)], [Pt(L1–3)(acac)], [Pt(L1–3)(8-Q)] (where L1–3 = N-octyl/dodecyl/hexadecyl-2-phenylquinoline-4-carboxamides; acac = acetylacetonate; 8-Q = 8-quinolinato) are described. Single crystal X-ray diffraction studies on [Pt(L1)(acac)] revealed a square planar coordination geometry with intermolecular Pt–Pt contacts at ca. 3.3 Å. The complexes were investigated using 195Pt{1H} NMR spectroscopy, revealing varied chemical shifts around ?Pt ?2800 ppm that were strongly dependent upon the specific coordination environment of Pt(II). Luminescence studies showed the complexes possess a phosphorescent character with tuneable emission wavelengths between 605 and 641 nm, and luminescent lifetimes up to ca. 450 ns. Supporting TD-DFT studies provided descriptions of the HOMO and LUMO energy levels of the key complex types, which generally correlated well with the experimental spectra. The contribution of the Pt(5d) centre to the calculated HOMOs was strongly ligand dependent, whilst the LUMOs were generally predicted to be localized over the quinoline component of the cyclometalated ligand.
0022-328X
87-93
Lowe, Juliette A.
8a5ee117-4f86-4ca6-8f65-80f32d530c8d
Stacey, Oliver J.
be15a0dd-6efe-4fa0-95da-3694e9a6cee6
Horton, Peter N.
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Pope, Simon J.A.
db9a489c-29ba-41cd-a96a-623bace0889d
Lowe, Juliette A.
8a5ee117-4f86-4ca6-8f65-80f32d530c8d
Stacey, Oliver J.
be15a0dd-6efe-4fa0-95da-3694e9a6cee6
Horton, Peter N.
154c8930-bfc3-495b-ad4a-8a278d5da3a5
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Pope, Simon J.A.
db9a489c-29ba-41cd-a96a-623bace0889d

Lowe, Juliette A., Stacey, Oliver J., Horton, Peter N., Coles, Simon J. and Pope, Simon J.A. (2016) Alkyl chain functionalised, cyclometalated platinum(II) complexes: syntheses, luminescence properties and X-ray crystal structure. Journal of Organometallic Chemistry, 805, 87-93. (doi:10.1016/j.jorganchem.2016.01.015).

Record type: Article

Abstract

The synthesis and characterisation of nine new monometallic heteroleptic platinum complexes [PtCl(L1–3)(DMSO)], [Pt(L1–3)(acac)], [Pt(L1–3)(8-Q)] (where L1–3 = N-octyl/dodecyl/hexadecyl-2-phenylquinoline-4-carboxamides; acac = acetylacetonate; 8-Q = 8-quinolinato) are described. Single crystal X-ray diffraction studies on [Pt(L1)(acac)] revealed a square planar coordination geometry with intermolecular Pt–Pt contacts at ca. 3.3 Å. The complexes were investigated using 195Pt{1H} NMR spectroscopy, revealing varied chemical shifts around ?Pt ?2800 ppm that were strongly dependent upon the specific coordination environment of Pt(II). Luminescence studies showed the complexes possess a phosphorescent character with tuneable emission wavelengths between 605 and 641 nm, and luminescent lifetimes up to ca. 450 ns. Supporting TD-DFT studies provided descriptions of the HOMO and LUMO energy levels of the key complex types, which generally correlated well with the experimental spectra. The contribution of the Pt(5d) centre to the calculated HOMOs was strongly ligand dependent, whilst the LUMOs were generally predicted to be localized over the quinoline component of the cyclometalated ligand.

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Accepted/In Press date: 12 January 2016
e-pub ahead of print date: 14 January 2016
Published date: 1 March 2016

Identifiers

Local EPrints ID: 393249
URI: http://eprints.soton.ac.uk/id/eprint/393249
ISSN: 0022-328X
PURE UUID: 6de53007-6d06-4948-b016-9a23858288a6
ORCID for Peter N. Horton: ORCID iD orcid.org/0000-0001-8886-2016
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 25 Apr 2016 10:08
Last modified: 15 Mar 2024 03:04

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Contributors

Author: Juliette A. Lowe
Author: Oliver J. Stacey
Author: Peter N. Horton ORCID iD
Author: Simon J. Coles ORCID iD
Author: Simon J.A. Pope

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