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AMX DAS-D-0406 User Manual Page 6

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Abstract
The intention of this work was the preparation of new ternary iodides of the rare earth elements
with alkaline earth cations. Reduction of LaI
3
with elemental strontium led to the first compound
of a ternary rare earth iodide with an alkaline earth cation. In SrLaI
4
and the isotypic BaLaI
4
chains of face sharing [LaI
8
] square-antiprisms are running parallel to [100]. The separation
of lanthanum and alkaline earth cations in different crystallographic positions can be explained
by the existence of a single electron in a 5d-state of the rare earth cation. Interactions between
these electrons of adjacent lanthanum ions led to the formation of [LaI
8
] polyhedral chains.
The alkaline earth cations are coordinated in the same way as the [LaI
8
]-polyhedras by iodide
to bridge adjacent chains of [LaI
8
]-polyhedra. In addition, the reaction of LaI
3
with elemental
strontium yielded in the formation of single crystals of LaI
2
.
Crystals of La
9
O
4
I
16
have been obtained by a side reaction of LaI
3
with barium. The crystal
structure of La
9
O
4
I
16
exhibits trans-edge connected chains of [La
4
O] tetrahedra running along
[101]. Layers of these chains are connected via isolated [LaI
8
] square-antiprisms along [010].
Reduction of PrI
3
with barium resulted in the formation of Ba
6
Pr
3
I
19
. In Ba
6
Pr
3
I
19
square-
antiprisms of [PrI
8
] are also found, which are connected in the same way as in BaLaI
4
and
SrLaI
4
, respectively, but with infinite chains interrupted after every third [PrI
8
] polyhedron by
cubic gaps to form isolated [Pr
3
I
16
] units. Adjacent [Pr
3
I
16
] units are connected via three
crystallographically different barium cations. By reduction of PrI
3
with strontium, Pr
2
I
5
was
obtained.
Reaction of ScI
3
with elemental strontium led to another phase in the system Sc / ScI
3
. Sc
0,87
I
2
crystallizes in the CdI
2
-type of structure where 87% of all octahedral vacancies are filled with
scandium cations.
Reduction of NdI
3
with strontium resulted in the formation of a mixed crystal with a
composition according to Sr
0,41
Nd
0,59
I
2
crystallizing with the SrI
2
type of structure .
First investigations of ternary reduced rare earth bromides with alkaline earths did not result
in a compound BaLaBr
4
. Reaction of barium with LaBr
3
led to La
4
OBr
7
which contains isolated
[La
4
O] tetrahedral units. These units are connected via four crystallographically different
bromide ions to form a three-dimensional network.
In the system Dy / DyI
3
single crystals of DyI
2
were obtained, whose crystal structure could be
determinated for the first time by single crystal diffractometry.
Attempts to synthesize one of the known modifications of PrI
2
have resulted in a cooling rate
dependent crystallization of the modifications IV and V.
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