The reactions of 7-azaindole with Al(CH3)3 have been investigated. Two new 7-azaindole
complexes, Al2(CH3)4(7-azain)2 (1) and Al2(CH3)2(7-azain)4 (2) have been isolated and
structurally characterized. Both complexes display a blue luminescence upon irradiation
by UV light. The introduction of alcohol and water into the reaction of 7-azaindole with
Al(CH3)3 resulted in the formation of several dinuclear and polynuclear complexes which
also emit in the blue region. The crystal structures of three new complexes from these
reactions, Al2(μ-OCH(CF3)2)(CH3)(7-azain)2(OCH(CF3)2)2 (3), Al3(μ3-O)(CH3)(7-azain)4(OCH(CF3)2)2 (4), and Al4(μ3-O)2(7-azain)6(OCH(CF3)2)2 (5), have been determined by X-ray
diffraction analyses. The 7-azaindole ligand in compounds 1−5 has the same bonding mode,
i.e., bridging two aluminum ions. The quantum yields for compounds 2 and 4 were
determined to be 0.54 and 0.31, respectively, relative to that of 9,10-diphenylanthracene in
cyclohexane. The emission lifetime for these compounds is in the order of 10−100 ns.
Molecular orbital calculations using Gaussian 94 methods on the neutral free ligand
(7-azainH), the deprotonated ligand (7-azain-), and compound 1 were performed, which
revealed that the aluminum ions in the complexes play a key role in stabilizing the ligand
and promoting the blue luminescence.
The synthesis of tertiary bismuth(III) complexes containing
amino or pyridyl functional
groups has been investigated. An improved synthesis for
Bi[p-C6H4(NMe2)]3
(1) has been
achieved. Two new complexes,
Bi[p-C6H4CH2(NPri
2)]3
(2) and
Bi[p-C6H4CH2N(2-Py)2]3
(3),
have been obtained. The bismuth(V) derivatives of compounds
1 and 3 have been synthesized
via chlorine oxidation of 1 and 3 and the
subsequent substitution reactions. Compounds
Bi[p-C6H4(NMe2)]3(O2CCF3)2
(5) and
Bi{p-C6H4[CH2N(2-Py2)]}3(O2CCH3)2
(7) were obtained
from the reactions of the corresponding dichloride complexes,
BiAr3Cl2, with the
appropriate
silver salt. NMR spectroscopic studies established that in
solution, compound 5 is fluxional
while compound 7 is rigid. A dinuclear complex
Bi2[p-C6H4(NMe2)]6Cl2(O)
(6) was isolated
as the major product when the dichloride complex
Bi[p-C6H4(NMe2)]3Cl2
was reacted with
NaOH in nondistilled reagent grade dichloromethane. A quaternary
bismuth(V) complex,
Bi[p-C6H4(NMe2)]4[PF6]
(8), was obtained in good yield when
Bi[p-C6H4(NMe2)]3Cl2
was
reacted with TlPF6 in a 1:2 ratio. A closely related
quaternary bismuth(V) complex
{Bi[p-C6H4(NMe2)]4}2[Ag2Cl4]
(9), which contains an unusual three-coordinate dinuclear
anion
Ag2Cl4
2-, was obtained as a
trace product from the reactions of
Bi[p-C6H4(NMe2)]3Cl2
with
silver salts. The crystal structures of compounds 1 and
5−9 were determined by single-crystal X-ray diffraction analyses.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.