Potassium Hydroxide → 871012-92-9

The strategy for a sample convergent synthesis of a highly branched first generation organometallic dendrimer of the invention is shown in FIGS. 1 and 2. Taking FIG. 1 as an example, 2-(4-iodophenyl)pyridine (1) was prepared in a 40% yield by reaction of the mono-lithiated 1,4-diiodobenzene with 2-fluoropyridine. Trimethylsilylacetylene was then coupled with (1) under Sonogashira conditions to afford 2-(4-trimethylsilylethynylphenyl)pyridine (2) in an 89% yield. The acetylene was easily deprotected with either tetra-n-butylammonium fluoride in tetrahydrofuran or by treatment with aqueous potassium hydroxide in a methanol/dichloromethane mixture. Both methods gave 2-(4-acetylenylphenyl)pyridine (3) in an isolated yield of 80%. The dendronised ligand (5) was then formed by reaction of 3 with 2,3,4,5-tetraphenylcyclopentadienone (4). The reaction was heated at 220° C. for two to three hours using diphenyl ether as the solvent after which (5) was isolated in a 93% yield. The complexation of (5) to form the fac-tris(2-phenylpyridyl)iridium (III) cored dendrimer utilised the standard two step procedure. In the first step 2.5 equivalents of (5) was reacted with iridium trichloride trihydrate in aqueous 2-ethoxyethanol heated at reflux to give a mixture of the bis-iridium bis-chloro dimer and unreacted ligand. This mixture was then reacted with an excess of (5) in the presence of silver trifluoromethylsulfonate in diglyme at 130° C. to give, after purification, the desired dendrimer (6) in a 63% yield for the two steps. Gel permeation chromatography (GPC) showed that the dendrimer was mono-disperse and the facial nature of the dendrimer was confirmed by 1H NMR by comparison with spectra reported for other dendrimers with fac-tris(2-phenylpyridyl)iridium (III) cores.

ORD record

ord-a33507bce9b541beba2fcca37aeb3f08

Source dataset

uspto-grants-2015_07

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US09078330B2