Reaction of [RGa(NMe
2)
2]
2, where R = Me, Et, Bu, and Hx, with ammonia at 150
C in anautoc
lave produced inso
lub
le white powders formu
lated as o
ligomers of [RGaNH]
n. The ana
logous reactionbetween NH
3 and MeGa[N(SiMe
3)
2]
2 at
low temperature (&
lt;25
C) formed an iso
lab
le intermediate, [MeGa(
-NH
2)N(SiMe
3)
2]
2, that was characterized using sing
le-crysta
l X-ray diffraction. Infrared spectroscopy andX-ray diffraction of the o
ligomers were consistent with a rod
like structure comprised of six-membered,[RGaNH]
3 rings stacked perpendicu
lar to the
long axis of the rod. The method of synthesis, formu
la, anddiffraction resu
lts suggested a structura
l simi
larity between the a
lky
l, [RGaNH]
n, and the previous
ly reportedhydride, [HGaNH]
n. The structura
l and e
lectronic properties of rods having the genera
l formu
la H
3[(HXYH)
3]
nH
3 (XY = GaN, GeC;
n = 1-9) were investigated using density functiona
l theory. Atomice
lectronegativity differences between the group 13/15 and 14/14 systems were found to p
lay importantro
les in the geometrica
l structures of the two rods and a
lso caused significant differences in the e
lectronicstructures. Energetica
lly, it was found to be increasing
ly favorab
le to add additiona
l cyc
lotriga
llazane ringsto the GaN rods, whi
le for the GeC rods, there was a rough
ly constant energy cost associated with eachadditiona
l ring. The e
lectric dipo
le moments of the GaN rods increased substantia
lly with
length; in theGeC rods, charge separation occurred to a much sma
ller extent and had a po
larization opposite to thatfound in GaN. In addition, increased dipo
le moments corre
lated with sma
ller e
lectronic excitation energies,as predicted by time-dependent density functiona
l theory. A
ll of the powders exhibited
luminescence in thevisib
le spectrum at room temperature. Structure observed in the photo
luminescence spectra of [HGaNH]
nand [MeGaNH]
n was interpreted as arising from rods of different
length.