Luminescent Properties of Lanthanide Nitrato Complexes with Substituted Bis(benzimidazolyl)pyridines Stéphane Petoud Jean-Claude G. Bünzli Kurt J. Schenk Claude Piguet 10.1021/ic961305a.s001 https://acs.figshare.com/articles/journal_contribution/Luminescent_Properties_of_Lanthanide_Nitrato_Complexes_with_Substituted_Bis_benzimidazolyl_pyridines/3617784 The protonated form of the ligand 2,6-bis(1‘-methylbenzimidazol-2‘-yl)pyridine crystallizes as its perchlorate salt (HL<sup>1</sup>)ClO<sub>4</sub> (<b>1</b>) in the orthorhombic system <i>Pbca</i>, with <i>a</i> = 13.976(3) Å, <i>b</i> = 14.423(3) Å, <i>c</i> = 19.529(4) Å, <i>Z</i> = 8. The proton is located on one benzimidazole N-atom, and the two N-methyl substituents lie on the same side of the pyridine N-atom (cisoid conformation). New 1:1 nitrato complexes of composition [Eu(NO<sub>3</sub>)<sub>3</sub>(L<i><sup>i</sup></i><sup></sup>)](solv‘)<i><sub>y</sub></i> have been isolated with L<sup>4</sup> (<b>4</b>), L<sup>6</sup> (<b>5</b>), L<sup>7</sup> (<b>6</b>), and L<sup>8</sup> (<b>7</b>), and their structural and photophysical properties are compared with those of the previously reported complexes [Eu(NO<sub>3</sub>)<sub>3</sub>(L<sup>1</sup>)(MeOH)] (<b>2</b>) and [Eu(NO<sub>3</sub>)<sub>3</sub>(L<sup>3</sup>)] (<b>3</b>). The crystal and molecular structure of [Eu(NO<sub>3</sub>)<sub>3</sub>(L<sup>7</sup>)(MeCN)]·2.5MeCN at 180 K (<b>6a</b>, triclinic, <i>P</i>1̄, <i>a</i> = 12.137(2) Å, <i>b</i> = 14.988(3) Å, <i>c</i> = 16.926(3) Å, α = 114.52(3)°, β = 98.28(3)°, γ = 103.99(3)°, <i>Z</i> = 2) shows a decacoordinated Eu<sup>III</sup> ion to six O-atoms from the nitrates, three N-atoms from L<sup>7</sup>, and one N-atom from a coordinated MeCN. The metal-centered luminescence arising upon ligand excitation in the solid state is analyzed in terms of nephelauxetic effects of the ligand and crystal field splitting of the <sup>7</sup>F<sub>1</sub> level. Quantum yields of 10<sup>-3</sup> and 10<sup>-4</sup> M solutions in MeCN are substituent dependent and may be rationalized by taking into account several factors, including the energy of the ligand singlet and triplet levels and the arrangement of the ligands in the first coordination sphere. We also show that the quantum yield of the ligand-centered luminescence decreases in the order L<sup>1</sup> > [La(NO<sub>3</sub>)<sub>3</sub>(L<sup>1</sup>)]MeOH > [La(L<sup>1</sup>)<sub>3</sub>](ClO<sub>4</sub>)<sub>3</sub>. 1997-03-26 00:00:00 protonated form nephelauxetic effects substituent ligand excitation L 8 L 7 L 4 MeCN 180 K HL 1 photophysical properties quantum yields Lanthanide Nitrato Complexes 7 F 1 level order L 1 cisoid conformation perchlorate salt triplet levels crystal field splitting Luminescent Properties MeOH complex ligand singlet decacoordinated Eu III ion coordination sphere system Pbca luminescence ClO 4