We have investigated the spin distribution and determined the magnetic exchange coupling J(ab) (defined according to the following Hamiltonian: H(spin) = -2J(ab)S(a).S(b)) for three arylethynyl-bridged organoiron(III) diradicals containing [(eta(2)-dppe)(eta(5)-C(5)Me(5))Fe(III)](+) fragments. Considering the distance separating the Fe(III) centers (>or=11 A), remarkably large intramolecular magnetic interactions between unpaired spins were found for two of them. Thus, an antiferromagnetic coupling (J(ab)) of ca. -190 cm(-1) was experimentally determined for the binuclear Fe(III) species featuring a 1,4-diethynylbenzene bridge 1[PF(6)](2), while a ferromagnetic interaction of over +150 cm(-1) was evidenced for its 1,3-substitued analogue 2[PF(6)](2). We also show that a much weaker interaction (0 > J(ab) >or= -1 cm(-1)) takes place in the 4,4'-biphenyl analogue of 1[PF(6)](2) (3[PF(6)](2)), evidencing that insertion of an additional 1,4-phenylene unit in the bridge severely disrupts the magnetic communication in these diradicals. With the help of NMR and density functional theory, the magnetic properties of these compounds were rationalized and compared to those of the corresponding mononuclear Fe(III) relatives 4[PF(6)] and 5[PF(6)]. Finally, it is shown that, for all of these dinuclear Fe(III) complexes, the structural changes between singlet and triplet spin isomers remain very small regarding the carbon-rich bridge. Thus, even for a strongly coupled diradical such as 1[PF(6)](2), a dominant diradicaloid character dominates the valence-bond description of the singlet state unpaired electrons.
The synthesis of new chromophore-based pyridine-dicarboxamide ligands and related D3 symmetric europium(III) complexes is described. The photophysical properties of the ligands and the complexes were thoroughly investigated and interpreted on the basis of theoretical calculations (TD-DFT). Finally, the luminescence of Eu(III) was sensitized by two-photon absorption of the ligand, illustrating the two-photon antenna effect phenomenon.
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