Heterometallic Chalcogenido Clusters Containing Lanthanides and Main Group Metals:  Emissive Precursors to Ternary Solid-State Compounds

Abstract

Heterometallic clusters containing lanthanides and the group 12 metals can be isolated as crystalline compounds in high yields. These products [(py)8Ln4M2Se6(SePh)4 (Ln = Er, Yb, Lu; M = Cd, Hg)] adopt a double cubane structure with the covalent M occupying an opposing pair of external metal sites. Both Er/M compounds are strongly emissive materials, with emission lifetimes of 1.41 ms (Er/Cd) and 0.71 ms (Er/Hg) and with the Er/Cd radiative quantum efficiency twice that of the Er/Hg compound. Thermal decomposition of the Er/Cd and Yb/Cd compounds at 650 degrees C give the ternary solid-state materials CdLn2Se4.

Lanthanide‐Containing Light‐Emitting Organic–Inorganic Hybrids: A Bet on the Future

“…[210] Amplification of emission by a factor of 1000 was observed. These results, obtained for polymer media, could be further improved in organic-inorganic hybrids, [211] Visible-light emissive active coatings have been demonstrated for different organic-inorganic hybrid systems. UV-sensitive coatings can emit light in all visible-range colors.…”

Oxoclusters of the Lanthanides Begin to Resemble Solid-State Materials at Very Small Cluster Sizes: Structure and NIR Emission from Nd(III)

“…These clusters can be quite emissive, if ligands with high-energy vibrational modes are excluded. For example, recent reports outlined the synthesis, characterization, and extraordinary properties of Er [17][18][19][20] and Nd 21 chalcogenido clusters. First noted was the 1.54 µm emission with 78% quantum efficiency from (THF) 14 Er 10 S 6 -(SeSe) 6 I 6 , and this was followed by the neodymium cluster (THF) 8 NdO 2 Se 2 (SePh) 16 (Nd8), which showed emission at 1349 and 1832 nm, the latter wavelength being unprecedented for a molecular Nd source.…”

Solvothermal Syntheses and Characterization of a Series of New Selenidostannates with Lanthanide Complexes as Counterions

“…Unsaturated TMCs that act as either decorating groups or bridging groups can bond directly to [Sn 2 Q 6 ] 4-anions to form a new class of organic hybrid chalcogenidostannates, as exemplified by [{Mn(en) 2 } 2 (l-en) (l-Sn 2 S 6 )] [11], [{M(tren)} 2 (l-Sn 2 S 6 )] (tren = tris(2-aminoethyl)amine; M = Ni and Co) [2a], and [M(tepa)] 2 (l-Sn 2 Se 6 ) (tepa = tetraethylenepentamine; M = Fe, Co, Mn) [12,13]. Compared with the overwhelming chalcogenido-stannates containing TMCs, lanthanoid chalcogenidostannates are less explored under mild solvothermal conditions [14][15][16], mainly because they are comparatively unstable with respect to heat, water, oxygen, and light [17]. More recently, we have attempted the preparation of lanthanoid chalcogenidostannates in chelating amine solutions by the solvothermal methods, and prepared a series of lanthanoid chalcogenidostannates containing [Sn 2 Q 6 ] 4-anions [Y 2 (dien) 4 (l-OH) 2 ]Sn 2 S 6 [18], (tetaH) 2 [Ln 2 (teta) 2 (tren) 2 (l-Sn 2 S 6 )]Sn 2 S 6 (Ln = Eu, Sm) [18], [Eu 2 (tepa) 2 (l-OH) 2 (l-Sn 2 S 6 )]-(tepa) 0.…”