Chemical Assembling of Heterometallic {Cd–M} (M=Li, Mg, Eu, Tb) Molecules with 3,5‐Di‐ <i>tert</i> ‐butylbenzoate Bridges and N‐Donor Ligands
Maxim A. Shmelev, Natalia V. Gogoleva, Alexey A. Sidorov, Yulia A. Nelyubina, F.M. Dolgushin, Julia К. Voronina, Mikhail A. Kiskin, Grigory G. Aleksandrov, Evgenia A. Varaksina, Ilya V. Taydakov, И.Л. Еременко
Abstract
Abstract It was shown that the reaction of potassium 3,5‐di‐ tert ‐butylbenzoate (Kbzo) and Cd(NO 3 ) 2 in EtOH gave the [Cd 3 (H 2 O)(EtOH) 3 (bzo) 6 ]⋅EtOH complex ( I ). The use of Li(bzo) or Mg(bzo) 2 salts in this reaction in the presence of excess 2,4‐lutidine or a stoichiometric amount of 1,10‐phenanthroline initiated the crystallization of the polymer [CdLi 2 (H 2 O)(EtOH) 2 (bzo) 4 ] n ( II ) containing no N‐donor ligands or trinuclear complexes [Cd 2 Mg(bzo) 6 (L) 2 ]⋅Solv (L, Solv=lut, 2EtOH ( III ); phen, 6CH 2 Cl 2 ( IV )) that included coordinated N‐donors. The use of Eu(bzo) 3 as the source of Ln ions in the presence of a stoichiometric amount of lut gave trinuclear carboxylates [EuCd 2 (H 2 O) 2 (EtOH) 2 (bzo) 7 ]⋅3EtOH ( V ) and [TbCd 2 (H 2 O)(EtOH) 3 (bzo) 7 ]⋅2EtOH⋅2.7H 2 O ( VI ) containing no lut molecules. It was found that the incorporation of coordinated N‐donors was observed only if a 10‐fold excess of pyridine or a stoichiometric amount of 2,2’‐dipyridyl was added to the reaction medium in the presence of Ln(NO 3 ) 3 ⋅6H 2 O (Ln=Eu, Tb) or Ln(bzo) 3 , respectively. In these cases, trinuclear {Cd−Ln} complexes were formed, which contained a terminal N‐donor ligand, [LnCd 2 (bzo) 6 (NO 3 )(py) 4 ]⋅1.5MeCN (Ln=Eu ( VII ), Tb ( VIII )), [EuCd 2 (H 2 O)(bzo) 7 (bpy) 2 ]⋅2THF⋅3H 2 O⋅MeCN ( IX ) and [TbCd 2 (H 2 O)(bzo) 7 (bpy) 2 ] ( X )). The structures of the new compounds were determined by single‐crystal X‐ray diffraction analysis. The complexes were characterized by luminescence spectroscopy, IR spectra, CHN‐analysis and fluorescence analysis.