A fresh look at the structural diversity of dibenzoylmethanide complexes of lanthanides

Abstract

Synthetic methods for dibenzoylmethanide lanthanide complexes as well as heterolanthanide ones were systematized revealing several species.

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

“…The significant broadening of the signals in 1 H NMR spectra of complexes 4 – 6 made them uninformative for identifying the paramagnetic metal species. However, 19 F NMR spectra proved to be suitable for the investigation of dissociation equilibrium,[6m], [8g], [8p] because they contained three characteristic signals of M[TbL 4 ], TbL 3 and ML. Two broadened singlets at δ F = 111.6 and 117.7 ppm correspond to tris‐ and tetrakis‐forms, respectively.…”

“…For a number of organic and organometallic compounds it is noted the important role of randomly distributed sites and disordered arrangement of substituents with weak (van der Waals forces only) interactions in the design of mechanoluminescent systems. [6i], [8a], [8r], , Sweeing and Rheingold reported the disorder of phenyl rings and cations in [Et 3 NH] + [Eu(dbm) 4 ] – provided a sufficient source of localized polarity to induce mechanoluminescence activity. [17c] In another case, the weak intermolecular interaction of fluoroalkyl groups promoted the formation of mechanoluminescent polymeric structure with fluorinated diketonates oriented along one plane.…”

“…The lanthanide(III) tetrakis(β‐diketonates) with the general formula (cation)[Ln(β‐diketonate) 4 ] have been extensively studied over the past decades . In their structure, four β‐diketonate ligands form the saturated coordination sphere around Ln III ion.…”

“…For instance, complexes [Na‐tetraglyme] + [Ln(hfa) 4 ] – and Na[Ln(hfa) 4 ] were successfully used as a single‐organic CVD source for NaLnF 4 films preparation. [6e], [6m] Partially fluorinated ligands enhance precursor volatility and increase the solubility of complexes providing their better crystallization . Moreover, the solvent coligands can be displaced from the coordination sphere because of the additional coordination of fluorine atoms with metal ions in heterometallic structures …”

Metal–Organic Frameworks Based on Group 3 and 4 Metals

“…Polynuclear Ln 3+ clusters attract increasing attention, as a result of their intriguing geometrical features and interesting properties related to magnetic, quantum computing and luminescent applications. The reported Ln 3+ clusters mainly include trinuclear (Ln 3 , Ln = Gd, Tb, Dy, Ho), [16,17] tetranuclear (Ln 4 , Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb), [18][19][20][21][22][23][24][25][26][27] pentanuclear (Ln 5 , Ln = Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb), [25] hexanuclear (Ln 6 , Ln = Pr, Ce, Eu, Gd, Tb, Dy, Er and Y), [27][28][29][30] octagon (Ln 8 , Ln = Gd, Tb, Dy, Ho), [31] nine-nuclear (Ln 9 , Ln = Nd, Sm, Eu, Gd, Tb, Dy, Ho), [32][33][34] eleven-nuclear (Ln 11 , Ln = Gd, Tb, Dy), [35] dodecanuclear (Ln 12 , Ln = Eu, Gd, Tb, Dy), [32,[36][37][38] hexadecanuclear (Ln 16 , Ln = Gd, Dy) clusters. [39] The number of Ln nuclei in Ln 3+ clusters was often controlled by the preferred coordination geometry of ligands [32] and the reaction environments.…”