Synthesis and luminescence spectroscopy of a series of [eta(5)-CpFe(CO)2] complexes containing 1,12-dicarba-closo-dodecaboranyl and -ylene ligands.

Three new cyclopentadienyliron dicarbonyl compounds, 1-[eta(5)-CpFe(CO)(2)]-1,12-C(2)B(10)H(11), 1-[[eta(5)-CpFe(CO)(2)]-1,12-C(2)B(10)H(10)-12-yl](2)Hg, and 1,12-[eta(5)-CpFe(CO)(2)](2)-1,12-C(2)B(10)H(10), composed of 1,12-dicarba-closo-dodecaborane as a ligand precursor were synthesized and found to be luminescent. The uncoordinated 1,12-C(2)B(10)H(12) bridging ligand precursor is luminescent with a band maximum at 25180 cm(-1), while the iron complexes luminesce at lower energies in the range 13120-14210 cm(-1). The lowest energy excited electronic state in the iron complexes is assigned to a ligand field transition of the iron chromophore. Cyclic voltammetry of 1,12-[eta(5)-CpFe(CO)(2)](2)-1,12-C(2)B(10)H(10) displays two discrete one-electron oxidations, and the luminescence maximum is red shifted from that observed in 1-[eta(5)-CpFe(CO)(2)]-1,12-C(2)B(10)H(11). Both of these observations suggest that the iron-centered chromophores are weakly coupled. In contrast, the 1-[[eta(5)-CpFe(CO)(2)]-1,12-C(2)B(10)H(10)-12-yl](2)Hg complex is uncoupled as is evident from the single oxidation process observed with cyclic voltammetry. The extinction coefficient of 1,12-[eta(5)-CpFe(CO)(2)](2)-1,12-C(2)B(10)H(10) is six times that of 1-[eta(5)-CpFe(CO)(2)]-1,12-C(2)B(10)H(11), while the extinction coefficient of 1-[[eta(5)-CpFe(CO)(2)]-1,12-C(2)B(10)H(10)-12-yl](2)Hg is only twice that of 1-[eta(5)-CpFe(CO)(2)]-1,12-C(2)B(10)H(11). These spectroscopic properties are explained in terms of two coupled antiparallel transition dipole moments.