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Synthesis, mesomorphism, and photophysics of 2,5-Bis(dodecyloxyphenyl)pyridine complexes of platinum(IV).

Parker, Rachel R. and Sarju, Julia P. and Whitwood, Adrian C. and Williams, J. A. Gareth and Lynam, Jason M. and Bruce, Duncan W. (2018) 'Synthesis, mesomorphism, and photophysics of 2,5-Bis(dodecyloxyphenyl)pyridine complexes of platinum(IV).', Chemistry - a European journal., 24 (71). pp. 19010-19023.

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.

Item Type:Article
Full text:(AM) Accepted Manuscript
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Status:Peer-reviewed
Publisher Web site:https://doi.org/10.1002/chem.201804026
Publisher 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.
Date accepted:06 August 2018
Date deposited:04 January 2019
Date of first online publication:13 September 2018
Date first made open access:13 September 2019

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