• Bulletin of the Korean Chemical Society
• /
• v.26 no.12
• /
• pp.1946-1952
• /
• 2005

New group 15 organometallic compounds, M$(phenanthrenyl)_3$ (M = P (1), Sb (2), Bi (3)) have been prepared from the reactions of 9-phenanthrenyllithium with $MCl_3$. A reaction of 9-(diphenylphosphino)phenanthrene with 2,6-diisopropylphenyl azide led to the formation of (phenanthrenyl)${(Ph)}_2P$=N-(2,6-$^iPr_2C_6H_3$) (4). The crystal structures of 2 and 4 have been determined by single-crystal X-ray diffractions, both of which crystallize with two independent molecules in the asymmetric unit. Compound 2 shows a trigonal pyramidal geometry around the Sb atom with three phenanthrenyl groups being located in a screw-like fashion with an approximately $C_3$ symmetry. A significant amount of CH- -$\pi$ interaction exists between two independent molecules of 4. The phosphorus center possesses a distorted tetrahedral environment with P-N bond lengths of 1.557(3)$\AA$ (P(1) N) and 1.532(3)$\AA$ (P(2)-N), respectively, which are short enough to support a double bond character. One of the most intriguing structural features of 4 is an unusually diminished bond angle of C-N-P, attributable to the hydrogen bonding of N(1)-H(5A) [ca. 2.49$\AA$ between two adjacent molecules in crystal packing. The compounds 1-3 show purple emission both in solution and as films at room temperature with emission maxima ($\lambda_{max}$) at 349, 366, and 386 nm, respectively, attributable to the ligand centered $\pi$ $\rightarrow$ $\pi^\ast$ transition in phenanthrene contributed by the lone pair electrons of the Gp 15 elements. Yet the nature of luminescence observed with 4 differs in that it originates from $\pi$ (diisopropylbenzene)-$\pi^\ast$ (phenanthrene) transitions with the $\rho\pi$contribution from the nitrogen atom. The emission maximum of 4 is red-shifted ranging 350-450 nm due to the internal charge transfer from the phenanthrenyl ring to the N-arylamine group as deduced from the ab initio calculations.

• Journal of the Korean Chemical Society
• /
• v.45 no.5
• /
• pp.442-447
• /
• 2001

The charge-transfer compound (OMTTF)AuCl$_4$ was prepared from the direct reaction of octamethylenethiafulvalene (OMTTF) with HAuCl$_4{\cdot}xH_2$O in THF. (OMTTF)$_2PtCl_4$, (OMTTF)_2IrCl_6{\cdot}2H_2$O, and (OMTTF)Os$Cl_5{\cdot}THF$ were also formed using $H_2PtCl_6{\cdot}xH_2O$, $H_2IrCl_6{\cdot}xH_2O$ and $H_2OsCl_6$, respectively. The prepared compounds were characterized by magnetic (EPR, magnetic susceptibility), spectroscopic (IR, UV-Vis), electrochemical (CV) methods, and the powdered electrical conductivity measurement. The powdered electrical conductivities at room temperature were ~$10^{-7}S{\cdot}cm^{-1}$. The experimental results show that $OMTTF^+$ monocation radicals exist in all of the prepared compounds. The redox potential of OMTTF supports that $OMTTF^+$ is relatively stable. The magnetic properties indicate that there are significant magnetic interactions between the localized odd electrons on the central metal (Ir and Os) ions and the odd electrons resided on $OMTTF^+$ cation radicals in both (OMTTF) $_2IrCl_6{\cdot}2H_2O$ and (OMTTF)$OsCl_5{\cdot}THF$.

• Microbiology and Biotechnology Letters
• /
• v.35 no.2
• /
• pp.163-172
• /
• 2007

This study was designed to investigate that inorganic germanium $(GeO_2)$ did not exist in germanium-fortified yeast or obtained to non-detectable value by current analytical methods and equipments. For this purpose, we achieved $GeO_2$ qualitative analysis protocol which could be the scientific basis of the study. Since reddish brown precipitate was formed from the reaction of $GeO_2$ with 1 equiv $NaBH_4$, and dark brown precipitate was also formed from the reaction of $GeO_2$ with 2 equiv $NaBH_4$, $GeO_2$ was qualitatively analyzed by observing these particular colored-precipitates. Because no color change was showed from the reaction between $NaBH_4$ and $SiO_2$, the color change could be caused by charge transfer transition on Ge-O and B binding properties. The reaction between $NaBH_4$ and germanium-fortified yeast did not show any color change and precipitate formation which meant no $GeO_2$ existed in germanium-fortified yeast. The reaction between $NaBH_4$ and supernatant specimen collected from the outside of dialysis membrane (MWCO 1,200 dalton) did not show any color change and precipitate formation. Therefore, we considered that the both germaniums in and outside of the dialysis membrane were organic germaniums. Germanium-fortified yeast which was biosynthesized organic germanium can be applied not only as a new functional material for improving health, prevention and treatment of chronic degenerative diseases including cancers, and the regulation of immune system, but also as a new materials.