• 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.

• The Korean Journal of Financial Management
• /
• v.26 no.4
• /
• pp.191-234
• /
• 2009

This study examined on the volatility feedback hypothesis through the use of threshold GARCH-in-Mean (GJR-GARCH-M) model developed by Glosten, Jaganathan, and Runkle (1993) in the stock markets of 14 emerging countries during the period of January, 1996 to May, 2009. On this study, I found successful evidences which can support the volatility feedback hypothesis through the following three estimation procedures. First, I found relatively strong positive relationship between the expected market risk premiums and their conditional standard deviations from the GARCH-M model in the basis of daily return on each representative stock market index, which is appropriate to investors' risk-averse preferences. Second, I can also identify the significant asymmetric time-varying volatility originated from the investors' differentiated reactions toward the unexpected market shocks by applying the GJR-GARCH-M model and further find the lasting positive risk aversion coefficient estimators. Third, I derived the negative signs of the regression coefficient of unpredicted volatility on the stock market return by re-applying the GJR-GARCH-M model after I controlled the positive effect of predicted volatility through including the conditional standard deviations from the previous GARCH-M model estimation as an independent explanatory variable in the re-applied new GJR-GARCH-M model. With these consecutive results, the volatility feedback effect was successfully tested to be effective also in the various emerging stock markets, although the leverage hypothesis turned out to be insufficient to be applied to another source of explaining the negative relationship between the unexpected volatility and the ex-post stock market return in the emerging countries in general.