Synthesis, characterisation and optical spectroscopy of platinum(II) di-ynes and poly-ynes incorporating condensed aromatic spacers in the backbone
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A series of protected and terminal dialkynes with extended.-conjugation through a condensed aromatic linker unit in the backbone, 1,4-bis(trimethylsilylethynyl) naphthalene, 2a, 1,4-bis(ethynyl)naphthalene, 2b, 9,10-bis(trimethylsilylethynyl)anthracene 3a, 9,10-bis(ethynyl)anthracene 3b, have been synthesized and characterized spectroscopically. The solid-state structures of 2a and 3a have been confirmed by single crystal X-ray diffraction studies. Reaction of two equivalents of the complex trans-[Ph(Et3P)(2)PtCl] with an equivalent of the terminal dialkynes 1,4-bis(ethynyl) benzene 1b and 2b-3b, in (Pr2NH)-Pr-i-CH2Cl2, in the presence of CuI, at room temperature, afforded the platinum(II) di-ynes trans-[Ph(Et3P)(2)Pt-C=C-R-C=C-Pt(PEt3)(2)Ph] (R = benzene-1,4-diyl 1c; naphthalene-1,4-diyl 2c and anthracene-9,10-diyl 3c) while reactions between equimolar quantities of trans-[((Bu3P)-Bu-n)(2)PtCl2] and 2b-3b under similar conditions readily afforded the platinum(II) poly-ynes trans-[-((Bu3P)-Bu-n)(2)Pt-C=C-R-C=C-](n) (R= naphthalene-1,4-diyl 2d and anthracene-9,10-diyl 3d). The Pt(II) diynes and poly-ynes have been characterized by analytical and spectroscopic methods, and the single crystal X-ray structures of 1c and 2c have been determined. These structures confirm the trans- square planar geometry at the platinum centres and the linear nature of the molecules. The di-ynes and poly-ynes are soluble in organic solvents and readily cast into thin films. Optical spectroscopic measurements reveal that the electron-rich naphthalene and anthracene spacers create strong donor - acceptor interactions between the Pt(II) centres and conjugated ligands along the rigid backbone of the organometallic polymers. Thermogravimetry shows that the di-ynes possess a somewhat higher thermal stability than the corresponding poly-ynes. Both the Pt(II) di-ynes and the poly-ynes exhibit increasing thermal stability along the series of spacers from phenylene through naphthalene to anthracene.