Novel Blue Phosphorescent Group 15 Compounds MR3 (M = P, Sb, Bi; R = p-(N-7-Azaindolyl)phenyl)

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• 作者：Youngjin Kang ; Datong Song ; Hartmut Schmider ; and Suning Wang
• 刊名：Organometallics
• 出版年：2002
• 出版时间：June 10, 2002
• 年：2002
• 卷：21
• 期：12
• 页码：2413 - 2421
• 全文大小：467K
• 年卷期：v.21,no.12(June 10, 2002)
• ISSN：1520-6041

文摘

New blue phosphorescent organometallic compounds of group 15, M[p-C₆H₄(N-7-azain)]₃with M = P (1), Sb (2), Bi (3) and 7-azain = 7-azaindolyl, have been synthesized from thereaction of MCl₃ with Li[p-C₆H₄(N-7-azain)]. The crystal structures of these new compoundshave been determined by single-crystal X-ray diffraction, which revealed that the group 15elements in all three complexes are in a trigonal-pyramidal environment with the bond anglesof C-M-C around the central atom decreasing from 1 to 3, attributed to the diminution ofs character of the M-C bond and the size increase of the central atom. All three compoundsare blue luminescent. Both fluorescent and phosphorescent emissions (_max = 371 nm, _max= 488 nm) were observed for compound 1 at 77 K. In contrast, at 77 K, only phosphorescencewas observed for compounds 2 and 3 (_max = 483 nm for 2; _max = 478 nm for 3), attributableto the increased heavy-atom effects. Experimental data and molecular orbital calculations(restricted Hartree-Fock methods) support the view that luminescences from all threecompounds are ligand-based emissions with contributions from the lone-pair electrons ofthe central atom. The orange Bi(V) compound Bi[p-C₆H₄(N-7-azain)]₃Cl₂ (4) was obtainedby the oxidation of 3 with PhI·Cl₂. Compound 4 displays a distorted-trigonal-bipyramidalstructure and a weak phosphorescence at _max = 510 nm at 77 K, which is most likely causedby charge-transfer transitions from the chloride ligand to the Bi(V) center.