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Chemical Assembling of Heterometallic {Cd–M} (M=Li, Mg, Eu, Tb) Molecules with 3,5‐Di‐ tert ‐butylbenzoate Bridges and N‐Donor Ligands
Author(s) -
Shmelev Maxim A.,
Gogoleva Natalia V.,
Sidorov Alexey A.,
Nelyubina Yulia A.,
Dolgushin Fyodor M.,
Voronina Yulia K.,
Kiskin Mikhail A.,
Aleksandrov Grigory G.,
Varaksina Evgenia A.,
Taydakov Ilya V.,
Eremenko Igor L.
Publication year - 2020
Publication title -
chemistryselect
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.437
H-Index - 34
ISSN - 2365-6549
DOI - 10.1002/slct.202001192
Subject(s) - chemistry , stoichiometry , molecule , ligand (biochemistry) , pyridine , medicinal chemistry , crystallization , stereochemistry , nuclear chemistry , crystallography , receptor , organic chemistry , biochemistry
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.