Competing excitation paths in luminescent heterobimetallic Ln-Al complexes: Unraveling interactions via experimental and theoretical investigations

Aluminium 8-Hydroxyquinolinate N-Oxide as a Precursor to Heterometallic Aluminium–Lanthanide Complexes

“…As described before, the relative stability of the structures can be evaluated as the difference between the Gibbs free energies of the heterometallic complexes [RE(hfac) 3 Al(qNO) 3 ] with respect to the fragments [Al(qNO) 3 ] and [RE(hfac) 3 ], and the same strategy will also be used with complexes in which two oxygen atoms bridge the two fragments. To simplify calculations for rare-earth complexes, La is commonly chosen for its closed-shell electronic structure [ 32 , 56 , 57 ], with the idea that this replacement does not significantly alter the geometrical properties. For these heterometallic complexes, by considering [La(hfac) 3 Al(qNO) 3 ], the structure with three bridging ligands is more stable than the one with two bridging ligands by about 4 kcal/mol (see Table 1 ).…”

“…We recently prepared a series of europium–aluminium compounds and studied the effect of aluminium ligands on the sensitized emission of europium. Combining photoluminescence experiments with density functional theory calculations, we explained the europium emission using a model involving two noninteracting excitation paths with the ligands coordinated to aluminium and europium, respectively [ 32 ]. Octahedral mononuclear aluminium complexes with oxygen donor monoanionic chelate ligands have been found suitable to be used as Lewis bases towards heterometallic complexes.…”

“…An alternative, attractive way to prepare heterobimetallic molecular complexes exploits the reaction of formally unsaturated lanthanide fragments [Ln(diketonate) 3 ] (with a diketonate carrying electron-withdrawing groups) with a mononuclear octahedral tris-chelate complex of a d or p metal centre acting base [22][23][24][25][26][27][28][29][30][31]. We recently prepared a series of europium-aluminium compound studied the effect of aluminium ligands on the sensitized emission of euro Combining photoluminescence experiments with density functional theory calcul we explained the europium emission using a model involving two noninter excitation paths with the ligands coordinated to aluminium and europium, respe [32]. Octahedral mononuclear aluminium complexes with oxygen donor monoa chelate ligands have been found suitable to be used as Lewis bases towards heterom complexes.…”

High-Nuclearity Ln210Al140 Clusters: Neonates of Open Hollow Dodecahedral Cage Families

“…Lanthanide–aluminum (Ln–Al) heterometallic complexes serve as potent catalysts for organic polymerization and as precursors for crafting highly crystalline LaAlO 3 perovskite , and luminescent materials. , However, unexpectedly, only a limited number of Ln–Al clusters have been documented thus far, − while high-nuclearity Ln–Al clusters, particularly those with highly symmetrical open hollow cage structures, remain undocumented. Here we report two unprecedentedly gigantic open hollow cage Ln–Al clusters, formulated as [Dy 210 ­Al 140 ­(μ 2 -OH) 210 ­(μ 3 -OH) 540 ­(OAc) 180 ­(H 2 O) 156 ](ClO 4 ) 120 ·(MeCN) 27 ·(H 2 O) 300 ( 1 ) and [Y 210 ­Al 140 ­(μ 2 -OH) 210 ­(μ 3 -OH) 540 ­(OAc) 180 ­(H 2 O) 156 ](ClO 4 ) 120 ·(MeCN) 28 ·(H 2 O) 420 ( 2 ).…”