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

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JournalChemistry : A European Journal
DateAccepted/In press - 13 Sep 2018
DateE-pub ahead of print - 15 Nov 2018
DatePublished (current) - 17 Dec 2018
Issue number71
Volume24
Pages (from-to)19010-19023
Early online date15/11/18
Original languageEnglish

Abstract

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(k2-N^CL)
2Cl(k1-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 f
10% and show vibrationally structured emission spectra,
lmax(0,0)=532 nm, strongly displaced to the red compared
to cis-[Pt(N^C-tolpy)Cl2]. Long luminescence lifetimes of
230 ms 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^Cppy)
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.

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© 2018 Wiley-VCH. This is an author-produced version of the published paper. Uploaded in accordance with the publisher’s self-archiving policy. Further copying may not be permitted; contact the publisher for details.

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