Novel lanthanide structures: Fluorinated alkoxides, chalcogenido alkoxides, fluorides, and oxychalcogenides

A number of novel lanthanide alkoxide species were synthesized with fluorinated ligands. This includes monomers with pentafluorophenol, (DME)2Ln(OC 6F5)3 (Ln = Nd, Er, Tm, Eu, and Yb), (py) 4Ln(OC6F5)3 (Ln = Eu, Tb, Er, Tm, Yb), and (THF)3Yb(OC6F5)3. Unique europium species, ((py)3Eu(CF3SO3)2) n, (DME)2Eu(micro-OC6F5)3Eu(micro-OC 6F5)3Eu(DME)2, and (DME)(C6F 5O)2Eu(micro-OC6F5)3Eu(DME) 2, were also produced. Most reactions proceeded by metathesis of lanthanide chalcogenolates, but direct redox reaction of elemental lanthanide with C 6F5OH or CF3SO3H catalyzed by Hg also proved to be viable routes. The Eu(II) trimer was only synthesized through direct oxidation of the metal with the alcohol. Photoluminescence of (DME) 2Ln(OC6F5)3 (Ln = Nd, Er, Tm) was tested, and they exhibited high quantum efficiency for lanthanide monomers.;Two series of dimers, (py)6Ln2(OC6F 5)2(micro-eta2-SS)2 (Ln = Sm, Eu, and Gd) and (py)6Ln2(CF3SO3) 2(Se)x (Ln = Sm, Tm, Yb, and Lu; x = 3 or 4), were synthesized via substitution of EPh-. The europium dimer is the first example of a Eu(III) molecular sulfido species which is extremely dark due to strong, broad LMCT from the sulfido. The selenidos display a conspicuous coordination change resulting from the relatively small difference in Ln ionic radii forming (py)6Ln2(CF3SO3)2(micro-eta 2-SeSe)(micro-Se) for small late lanthanides and (py)6Ln 2(CF3SO3)2(micro-eta2-Se) 2 for larger early lanthanides.;Three fluorido clusters were synthesized without the use of traditional fluoride sources. (DME)6(py)6Nd18(C 6F5O)18 F24O3S3 was produced from a reaction of neodymium phenylselenolate with C6F 5OH and sulfur. (py)8Yb4F8(CF 3SO3)4 and (DME)4Tb4(CF 3SO3)6F2S2 were synthesized from lanthanide chalcogenolates, elemental chalcogens, and CF3SO 3H. Cleavage of C-F bonds to form these clusters appears to be a slow reaction. Most reactions producing them took several months.;Lanthanide oxychalcogenido clusters were produced from reacting lanthanide chalcogenolates with pySO3 or TeO2 and Te. (THF) 8Ln8O2S2(SePh)16 (Ln = Ce, Nd) clusters were synthesized from "Ln(SePh)3" and pySO3. Reactions of "Ln(TePh)3", TeO 2 and Te produced [(py)5Ln3O(Te2) 3(TePh)][(py)7Ln4Te(Te2)2(Te 2Te(Ph)Te2)(TePh)] (Ln = Ho, Er), [(etpy)11Ho 6O4Te4TePh] [Hg(TePh)3] and [(4etpy) 12Yb6O4Te4][Hg(TePh)3] [(TePh) 3].