Chemical Assembling of Heterometallic {Cd–M} (M=Li, Mg, Eu, Tb) Molecules with 3, 5‐Di‐tert‐butylbenzoate Bridges and N‐Donor Ligands. Issue 28 (24th July 2020)

• Record Type: Journal Article
• Authors: 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.
• Is Part Of: ChemistrySelect. Volume 5:Issue 28(2020)
• Page Start: 8475
• Page End: 8482
• Publication Date: 2020-07-24
• Subjects: cadmium-lanthanide complexes -- 3, 5-di-tert-butylbenzoate anions -- luminescence -- synthesis -- X-ray diffraction; Chemistry -- Periodicals; 540.5
• DOI: 10.1002/slct.202001192
• Languages: English
• ISSNs: 2365-6549

Abstract

Abstract: It was shown that the reaction of potassium 3, 5‐di‐ tert ‐butylbenzoate (Kbzo) and Cd(NO3 )2 in EtOH gave the [Cd3 (H2 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 [CdLi2 (H2 O)(EtOH)2 (bzo)4 ] n (II ) containing no N‐donor ligands or trinuclear complexes [Cd2 Mg(bzo)6 (L)2 ]⋅Solv (L, Solv=lut, 2EtOH (III ); phen, 6CH2 Cl2 (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 [EuCd2 (H2 O)2 (EtOH)2 (bzo)7 ]⋅3EtOH (V ) and [TbCd2 (H2 O)(EtOH)3 (bzo)7 ]⋅2EtOH⋅2.7H2 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(NO3 )3 ⋅6H2 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, [LnCd2 (bzo)6 (NO3 )(py)4 ]⋅1.5MeCN (Ln=Eu (VII ), Tb (VIII )), [EuCd2 (H2 O)(bzo)7 (bpy)2 ]⋅2THF⋅3H2 O⋅MeCN (IX ) and [TbCd2 (H2 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. Abstract : Cd(II) forms a linear complex {Cd3 } with 3, 5‐di‐ tert ‐butylbenzoate‐anions that in the presence of N‐donor ligands can be reorganized to heterometallic compounds with metal core {CdLi2 }, {Cd2 Mg} and {Cd2 Ln}. The composition of the compounds can be manipulated by the amount of added N‐donor. Structures of complexes were approved by XRD or PXRD. Photoluminescent properties were studied for {Cd2 Ln} compounds.