Synthesis of bipyridine and terpyridine based ruthenium metallosynthons for grafting of multiple pyrene auxiliaries

The synthesis of novel ruthenium(II) bipyridine or terpyridine complexes bearing an increasing number of pyrene or toluyl moieties is described. The ruthenium complexes are constructed in a first step with ligands bearing the required bromine functions, followed in a second step by stepwise grafting of 1-ethynylpyrene or 4-ethynyltoluene promoted by Pd(0). A complex bearing a protected triethylsilylacetylene function was also prepared. In situ deprotection of this function with K2CO3 and cross-coupling with 1-bromopyrene afforded a soluble complex in which two pyrene moieties are linearly linked via ethynyl spacers to one of the bipyridine ligands. These highly coloured complexes exhibit well defined absorption and emission properties in solution at both rt and 77 K.