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http://dx.doi.org/10.5012/bkcs.2005.26.12.1946

Synthesis and Structural Characterization of Main Group 15 Organometallics R3M and R(Ph)2P(=N-Ar)(M = P, Sb, Bi; R = phenanthrenyl; Ar = 2,6-iPr2-C6H3)  

Lee, Eun-Ji (Department of Applied Chemistry, Kyungpook National University)
Hong, Jin-Seok (Department of Applied Chemistry, Kyungpook National University)
Kim, Tae-Jeong (Department of Applied Chemistry, Kyungpook National University)
Kang, Young-Jin (Division of Science Education, Kangwon National University)
Han, Eun-Me (Faculty of Applied Chemical Engineering, Chonnam National University)
Lee, Jae-Jung (Faculty of Applied Chemical Engineering, Chonnam National University)
Song, Ki-Hyung (Department of Chemistry, Korea National University of Education)
Kim, Dong-Uk (Department of Science Education, Daegu National University of Education)
Publication Information
Bulletin of the Korean Chemical Society / v.26, no.12, 2005 , pp. 1946-1952 More about this Journal
Abstract
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.
Keywords
Group 15 organometallics; M(phenanthrenyl)$_3$; (Phenanthrenyl)(Ph)$_2$P=NAr;
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