The Impact of the Alkali Metal Ion on the Crystal Structure and (Mechano)luminescence of Terbium(III) Tetrakis(β‐diketonates)

Abstract

The novel terbium(III) tetrakis(β‐diketonates) M[TbL4] with different alkali metal counterions (Na, K, Cs) based on functionalized trifluoromethylated β‐diketonate are reported. An efficient approach to alkali metal β‐diketonates ML (M = Na, K, Cs) is proposed, which does not require the alkaline media promoting the destruction of 1,3‐dicarbonyl compounds. The transformation of lithium β‐diketonate LiL into the corresponding alkali metal β‐diketonate ML has been achieved under mild conditions using alkali metal fluorides. Organic ligand generates the multiplicity of coordination modes through a diketonate fragment, methoxy group and trifluoromethyl substituent. The alkali metal ion changes the geometry of coordination environment of the terbium(III) ion and affects the crystal packing of complexes. The additional coordination centers in the ligand coupled with a small atomic radius of sodium ion resulted in a construction of a rare example of discrete lanthanide tetrakis(β‐diketonate) Na[TbL4]. Moreover, this complex exhibited bright luminescence and mechanoluminescence in contrast to polymeric TbIII tetrakis(β‐diketonates) with K and Cs.

Alkali Metal Carbatrane Compounds [TismPriBenz]M: Synthesis and Structural Characterization of a Complete Series of Monomeric Alkali Metal Alkyl Compounds

“…Precedent for the formation of [Tism Pr i Benz ]Cs by this approach is provided by O’Hara’s method for the synthesis of Cs­[N­(SiMe 3 ) 2 ] via reaction of Li­[N­(SiMe 3 ) 2 ] with CsF . A noteworthy feature of O’Hara’s method is that it eliminates the need to use either elemental cesium or organocesium reagents for the synthesis of amide derivatives. , The favorable metathesis between a lithium complex and CsF derives from the low solubility of LiF and has been employed in other systems. , …”

New Luminescent Lanthanide Tetrakis‐Complexes NEt4[LnL4] Based on Dimethyl‐N‐Benzoylamidophosphate

“…In some works, it was shown that the nature of cationic counterparts strongly influences the crystal structure and packing of the complexes as well as their physical properties. [35][36][37] In this work, we report the synthesis, structural characteristics, thermal, and luminescence properties of new dimethyl-Nbenzoylamidophosphate (HL) based lanthanide tetrakis-complexes NEt 4 [LnL 4 ] (Ln 3 + = La, Nd, Sm, Eu, Gd, Tb, Dy) (Scheme 1). Dimethyl-N-benzoylamidophosphate was shown to be a good lanthanide luminescence sensitizer [17,38] and a versatile ligand, which can bind metal ions in different modes.…”

“…In their structure, a lanthanide ion is surrounded by four ligands forming a LnO 8 environment and the cationic counterparts are typically alkali metal ions or positively charged N, P‐organic cations. In some works, it was shown that the nature of cationic counterparts strongly influences the crystal structure and packing of the complexes as well as their physical properties [35–37] …”

A One‐Pot Synthesis of “K(hfa) glyme” Adducts: Effect of the Polyether Length on the Ion Coordination Sphere

“…Finally, the Cambridge Structural database (CSD, v 5.41, update 2 May 2020) [38] was used to retrieve similar potassium complexes; just one structure was found containing a related CF 3 -β-diketonate ligand (L in the following). [39] Also in the case of the KL complex (CSD Refcode = COYPUE) a 1D polymer is formed. The K••••K distances observed in 1, 2 and 4 are comparable with those published for COYPUE (K••••K distances range = 3.552-4.246 Å).…”