| Abstract
| - A new series of bis(alkynyl) gold(I) and mercury(II) d10 complexes incorporating fluorenyl-based linking units are reported. The binuclear complexes [LAuC⋮CRC⋮CAuL] and theirisoelectronic mercury(II) congeners [R‘HgC⋮CRC⋮CHgR‘] (L = tertiary phosphines; R =fluorene-2,7-diyl, dihexylfluorene-2,7-diyl, 9-((ferrocenylphenylene)methylene)fluorene-2,7-diyl, fluoren-9-one-2,7-diyl, 9-(dicyanomethylene)fluorene-2,7-diyl; R‘ = Me, Ph) wereprepared in very good yields by the base-catalyzed dehydrohalogenation reaction of thecorresponding metal chloride precursors with the appropriate diethynylfluorene derivativesHC⋮CRC⋮CH at room temperature. All the compounds have been fully characterized byFTIR, NMR and electronic absorption spectroscopies and FAB mass spectrometry. The solid-state molecular structures of [Ph3PAuC⋮CRC⋮CAuPPh3] (R = 9,9-dihexylfluorene-2,7-diyl,fluoren-9-one-2,7-diyl) and [MeHgC⋮CRC⋮CHgMe] (R = fluoren-9-one-2,7-diyl) have beendetermined crystallographically, the last of which represents the first dimercury diacetylideto be structurally characterized. Absorption studies suggest that it is possible to fine-tunethe optical gap of this class of materials by modifying the electronic properties of thesubstituent at the 9-position of the central fluorene spacer. The solution redox chemistry ofthese fluorene-linked binuclear complexes as revealed by cyclic voltammetry indicates somedegree of electronic communication between the 9-substituent of the fluorenyl ring and theterminal metal groups via the conjugated alkynyl bridge. Most of the complexes in this studyhave been shown to exhibit rich photophysical behavior, and a discussion on their emissionproperties in terms of the nature of metal groups and their auxiliary ligands as well as thefluorene spacer was made.
- A new family of binuclear gold(I) and mercury(II) derivatives of diethynylfluorenes is reported. Their electronic, luminescent, and redox properties have been investigated as a function of the metal groups and their auxiliary ligands as well as the peripheral substituents of the central fluorene spacer.
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