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Synthesis, Mesomorphism, and Photophysics of 2,5-Bis(dodecyloxyphenyl)pyridine Complexes of Platinum(IV)

Parker, Rachel R.; Sarju, Julia P.; Whitwood, Adrian C.; Williams, J.A. Gareth; Lynam, Jason M.; Bruce, Duncan W.

Synthesis, Mesomorphism, and Photophysics of 2,5-Bis(dodecyloxyphenyl)pyridine Complexes of Platinum(IV) Thumbnail


Authors

Rachel R. Parker

Julia P. Sarju

Adrian C. Whitwood

Jason M. Lynam

Duncan W. Bruce



Abstract

It has been shown for the first time that the PtIV complex cis‐[Pt(N^C‐tolpy)2Cl2] (tolpy=2‐(4‐tolyl)pyridinyl) can be prepared in a one‐pot reaction from K2[PtCl4], although analogous complexes containing 2,5‐bis(4‐dodecyloxyphenyl)pyridine (=HL) could be prepared using existing routes. The resulting complexes cis‐[Pt(N^C‐L)2Cl2] are liquid crystals and small‐angle X‐ray scattering suggests formation of a lamellar mesophase. Surprisingly, heating [Pt(κ2‐N^C‐L)2Cl(κ1‐N^C‐LH)] also leads to a mesomorphic compound, which results from thermally induced oxidation to cis‐[Pt(N^C‐L)2Cl2] and what is presumed to be another geometric isomer of the same formula. The PtIV complexes are quite strongly luminescent in deoxygenated solution, with φ≈10 % and show vibrationally structured emission spectra, λmax(0,0)=532 nm, strongly displaced to the red compared to cis‐[Pt(N^C‐tolpy)Cl2]. Long luminescence lifetimes of 230 μs are attributed to a lower degree of metal character in the excited state accompanying the extension of conjugation in the ligand. There is no significant difference between the emission properties of the bromo‐ and chloro‐complexes, in contrast with the known complexes cis‐[Pt(N^C‐ppy)X2], where the quantum yield for X=Br is some 30 times lower than for X=Cl (ppyH=2‐phenylpyridine). The lower energy of the excited state in the new complexes probably ensures that deactivating LLCT/LMCT states remain thermally inaccessible, even when X=Br.

Citation

Parker, R. R., Sarju, J. P., Whitwood, A. C., Williams, J. G., Lynam, J. M., & Bruce, D. W. (2018). Synthesis, Mesomorphism, and Photophysics of 2,5-Bis(dodecyloxyphenyl)pyridine Complexes of Platinum(IV). Chemistry - A European Journal, 24(71), 19010-19023. https://doi.org/10.1002/chem.201804026

Journal Article Type Article
Acceptance Date Aug 6, 2018
Online Publication Date Sep 13, 2018
Publication Date Sep 13, 2018
Deposit Date Jan 3, 2019
Publicly Available Date Sep 13, 2019
Journal Chemistry - A European Journal
Print ISSN 0947-6539
Electronic ISSN 1521-3765
Publisher Wiley
Peer Reviewed Peer Reviewed
Volume 24
Issue 71
Pages 19010-19023
DOI https://doi.org/10.1002/chem.201804026

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Copyright Statement
This is the accepted version of the following article: Parker, Rachel R., Sarju, Julia P., Whitwood, Adrian C., Williams, J. A. Gareth, Lynam, Jason M. & Bruce, Duncan W. (2018). Synthesis, Mesomorphism, and Photophysics of 2,5-Bis(dodecyloxyphenyl)pyridine Complexes of Platinum(IV). Chemistry - A European Journal 24(71): 19010-19023 which has been published in final form at https://doi.org/10.1002/chem.201804026. This article may be used for non-commercial purposes in accordance With Wiley Terms and Conditions for self-archiving.







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