ABSTRACT
A series of cyano-bridged homotrinuclear Re(I) complexes with the general formula of {[Re]'[Re][Re]'}+ {[Re]' = -[ReI(CO)2(LL)(X)]; [Re] = -[(NC)ReI(CO)2(phen)(CN)]-; LL = diimine, diphosphine, or two carbonyl ligands; X = triphenylphosphine or carbonyl ligand} and the corresponding mononuclear complex analogues were synthesized. The structures of most of the trinuclear Re(I) complexes have been determined by X-ray crystallography. The relative orientations of peripheral to central Re(I) units in these structures vary considerably. The photophysical properties of these trinuclear Re(I) complexes have been examined. Except for the trinuclear Re(I) complex with Br2phen ligand, all the other triads display orange to red photoluminescence derived from the 3MLCT [dπ(Re) â π*(phen)] origin of the central Re(I) unit, suggestive of efficient energy transfer between the peripheral chromophores and the central unit. In addition to the efficient energy transfer processes between the Re(I) chromophores in these trinuclear complexes, the ability of the [NC-Re-CN] bridging ligands for electronic coupling between the rhenium metal centers is evidenced by ca. 0.2-0.3 V separation of the two rhenium metal-based oxidation potentials of the chemically equivalent peripheral units.
ABSTRACT
New classes of tunable rhenium(I) diimine luminophores with formula of [Re(CO)(CNR)(3)(N-N)]PF(6) and [Re(CO)(L(x))(CNC(6)H(4)Cl-4)(2)(1,10-phenanthroline)]PF(6), (R = C(6)H(5), 4-BrC(6)H(4), 4-ClC(6)H(4), 4-MeOC(6)H(4), 2,6-(i)Pr(2)C(6)H(3); N-N = 1,10-phenanthroline, 5,6-dibromo-1,10-phenanthroline, 4,4'-di-tert-butyl-2,2'-bipyridine; L(x) = MeCN, pyridine and PPh(3)) have been synthesized. Different synthetic routes including photo-ligand substitution and thermal carbonyl ligand substitution through the oxidative decarbonylation with trimethyl amine N-oxide, for the facial and meridional isomeric forms of [Re(CO)(CNR)(3)(N-N)]PF(6) were investigated. On the basis of these synthetic strategies, different ligand modification and functionalization of the rhenium(I) diimine luminophores with tailored excited state properties could be readily achieved. The structures of both facial and meridional conformations of [Re(CO)(CNR)(3)(N-N)]PF(6) and the complex precursors fac-[Re(CO)(3)(CNC(6)H(3)(i)Pr-2,6)(3)]OTf were determined by X-ray crystallography. These complexes display an orange to red (3)MLLCT [dπ(Re) â π*(N-N)] phosphorescence at room temperature. Detailed photophysical investigations revealed that the physical, photophysical, electrochemical, and excited state properties can be fine-tuned and tailored through the modifications of the substituents on isocyanide or diimine ligands.
