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The Pt-Organometallic Version of Perigraniline: Going Blue

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Abstract

Four conjugated push–pull organometallic polymers ([Pt]-AQ)n ([Pt] = trans-bis(phenylacetylene)bis(tributylphosphine)platinum(II); AQ = 2-bromo-, 2,6-dibromo-, 2,6-diamino-, and unsubstituted anthraquinone diimine) were prepared and characterized by UV–vis spectroscopy and electrochemistry. A low-energy charge transfer, CT, band ([Pt]*→AQ; confirmed by density functional theory calculations), was found in the 445–500 nm window rather than the expected red-shifted range above 630 nm. X-ray structures of four model compounds reveal that steric hindrance induces large dihedral angles between the C6H4 and N[DOUBLE BOND]CC2 planes, rendering π-orbital overlap difficult between the [Pt] and AQ units. The position of the CT band is mainly driven the reduction potential of the anthraquinone diimine unit.

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