New Fluorinated Stannic Compounds as Precursors of F-Doped SnO(2) Materials Prepared by the Sol-Gel Route.
Dialkoxydi(beta-diketonate)tin(IV) compounds react either with difluorodi(beta-diketonate)tin(IV) or with butanoyl fluoride to yield novel tin complexes Sn(OR(1))F(R(2)COCHCOR(2))(2) 1 (R(1) = tert-amyl, isopropyl, ethyl; R(2) = methyl, tert-butyl). Multinuclear (1)H, (13)C, (19)F, and (119)Sn NMR spectroscopic characterization showed that complexes 1 are octahedral in solution with a cis configuration for the fluorine and the alkoxide group. Kinetics of configurational rearrangements were studied by variable-temperature (13)C NMR spectroscopy. The hydrolytic behavior of 1 was determined for different hydrolysis ratios h = [H(2)O]/[1]. For R(1) = tert-amyl, a dimeric fluorinated species was mainly obtained for h = 0.5, and addition of 2 mol equiv of water led to a fluorinated stannic oxopolymer soluble in CH(3)CN. In the latter case, the powder obtained after solvent elimination and treatment in air at 550 degrees C consisted of crystalline SnO(2) cassiterite particles containing the required amount (3 mol %) of doping fluorine and exhibiting electronic conductivity comparable to that of Sn-doped In(2)O(3). Complexes 1 are the first precursors of F-doped SnO(2) materials prepared by the sol-gel route.
Gamard
A.
A
Laboratoire de Chimie Organique et Organométallique, UMR 5802 CNRS, Université Bordeaux I, 351 Cours de la Libération, F-33405 Talence Cedex, France, and Institut de Chimie de la Matière Condensée de Bordeaux, UPR 9048 CNRS, Château Brivazac, Avenue du Docteur A. Schweitzer, F-33608 Pessac Cedex, France.
Jousseaume
B.
B
Toupance
T.
T
Campet
G.
G