10.1021/om020220g.s001
Youngjin Kang
Youngjin
Kang
Datong Song
Datong
Song
Hartmut Schmider
Hartmut
Schmider
Suning Wang
Suning
Wang
Novel Blue Phosphorescent Group 15 Compounds MR<sub>3</sub>
(M = P, Sb, Bi; R = <i>p</i>-(<i>N</i>-7-Azaindolyl)phenyl)
American Chemical Society
2002
Bi
azain
Novel Blue Phosphorescent Group 15 Compounds MR 3
group 15 elements
compound
C 6 H 4
λ max
Compound 4 displays
nm
77 K
2002-05-14 00:00:00
Journal contribution
https://acs.figshare.com/articles/journal_contribution/Novel_Blue_Phosphorescent_Group_15_Compounds_MR_sub_3_sub_M_P_Sb_Bi_R_i_p_i_-_i_N_i_-7-Azaindolyl_phenyl_/3772446
New blue phosphorescent organometallic compounds of group 15, M[<i>p</i>-C<sub>6</sub>H<sub>4</sub>(<i>N</i>-7-azain)]<sub>3</sub>
with M = P (<b>1</b>), Sb (<b>2</b>), Bi (<b>3</b>) and 7-azain = 7-azaindolyl, have been synthesized from the
reaction of MCl<sub>3</sub> with Li[<i>p</i>-C<sub>6</sub>H<sub>4</sub>(<i>N</i>-7-azain)]. The crystal structures of these new compounds
have been determined by single-crystal X-ray diffraction, which revealed that the group 15
elements in all three complexes are in a trigonal-pyramidal environment with the bond angles
of C−M−C around the central atom decreasing from <b>1</b> to <b>3</b>, attributed to the diminution of
s character of the M−C bond and the size increase of the central atom. All three compounds
are blue luminescent. Both fluorescent and phosphorescent emissions (λ<sub>max</sub> = 371 nm, λ<sub>max</sub>
= 488 nm) were observed for compound <b>1</b> at 77 K. In contrast, at 77 K, only phosphorescence
was observed for compounds <b>2</b> and <b>3</b> (λ<sub>max</sub> = 483 nm for <b>2</b>; λ<sub>max</sub> = 478 nm for <b>3</b>), attributable
to the increased heavy-atom effects. Experimental data and molecular orbital calculations
(restricted Hartree−Fock methods) support the view that luminescences from all three
compounds are ligand-based emissions with contributions from the lone-pair electrons of
the central atom. The orange Bi(V) compound Bi[<i>p</i>-C<sub>6</sub>H<sub>4</sub>(<i>N</i>-7-azain)]<sub>3</sub>Cl<sub>2</sub> (<b>4</b>) was obtained
by the oxidation of <b>3</b> with PhI·Cl<sub>2</sub>. Compound <b>4</b> displays a distorted-trigonal-bipyramidal
structure and a weak phosphorescence at λ<sub>max</sub> = 510 nm at 77 K, which is most likely caused
by charge-transfer transitions from the chloride ligand to the Bi(V) center.