Luminescent d8 and d10 metal complexes of anthracenyl and pyrenyl ligands

Abstract

<P>9,10-BIS(DIPHENYLPHOSPHINO)ANTHRACENE UNDERGOES REGIOSELECTIVE DOUBLE CYCLOMETALATION WITH PLATINUM(II) TO GENERATE THE GEOMETRICAL SYN-AND ANTI-ISOMERS; AND AN ELECTROPHILIC SUBSTITUTION PATHWAY IS PROPOSED FOR THE REACTION. SPECTROSCOPIC STUDY SHOWS THAT THE METAL IONS CAN PERTURB THE ELECTRONIC STRUCTURE OF THE ANTHRACENYL RING SIGNIFICANTLY. THERE IS AN APPARENT ABSENCE OF HEAVY-ATOM EFFECTS ON THE S1-T2 INTERSYSTEM CROSSING IN THE DICYCLOMETALATED COMPLEXES, POSSIBLY DUE TO A WIDENED GAP BETWEEN THE S1 AND T2 STATES.</P><P>1-(DIPHENYLPHOSPHINO)PYRENE AND 1,6-BIS(DIPHENYLPHOSPHINO)PYRENE (16PYP) UNDERGO FACILE SINGLE AND DOUBLE CYCLOMETALATION, RESPECTIVELY, WITH PD(II) AND PT(II). THE SINGLY- AND DOUBLY-CYCLOPLATINATED COMPLEXES DISPLAY VERY INTENSE LONG-LIVED RED PHOSPHORESCENCE IN SOLUTION INDUCED BY THE INTERNAL HEAVY-ATOM EFFECT OF PLATINUM(II) IONS. </P><P>16PYP REACTS WITH AG(I) AND CU(I) TO FORM DIMERIC RINGS, WHICH ARE BELIEVED TO BE THE FIRST KIND OF PYRENOPHANES ASSEM