Investigation of the structure and magnetism in lanthanide β-triketonate tetranuclear assemblies

Article abstract of DOI:10.1080/00958972.2016.1180375

The preparation of discrete tetranuclear lanthanide/alkali metal (Ae) assemblies bearing a tribenzoylmethane ligand (LH) is discussed. These assemblies have the general formula [Ln(Ae·HOEt)(L)₄]₂, where Ln³⁺ = Gd³⁺

Full text of DOI:10.1080/00958972.2016.1180375

Journal of Coordination Chemistry
ISSN: 0095-8972 (Print) 1029-0389 (Online) Journal homepage: http://www.tandfonline.com/loi/gcoo20
Investigation of the structure and magnetism in
lanthanide β-triketonate tetranuclear assemblies
Brodie L. Reid, Robert C. Woodward, Rebecca O. Fuller, Alexandre N.
Sobolev, Brian W. Skelton, Mark I. Ogden & Massimiliano Massi
To cite this article: Brodie L. Reid, Robert C. Woodward, Rebecca O. Fuller, Alexandre N.
Sobolev, Brian W. Skelton, Mark I. Ogden & Massimiliano Massi (2016): Investigation of the
structure and magnetism in lanthanide β-triketonate tetranuclear assemblies, Journal of
Coordination Chemistry, DOI: 10.1080/00958972.2016.1180375
To link to this article: http://dx.doi.org/10.1080/00958972.2016.1180375
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Date: 18 June 2016, At: 15:10

Journal of Coordination Chemistry, 2016
ꢁꢁp://ꢂx.ꢂꢃꢄ.ꢃꢅg/10.1080/00958972.2016.1180375
ꢀ
Investigation of the structure and magnetism in lanthanide
β-triketonate tetranuclear assemblies
a
b
c
d
Brodie L. Reid , Robert C. Woodward , Rebecca O. Fuller , Alexandre N. Sobolev ,
d
a
a
Brian W. Skelton , Mark I. Ogden and Massimiliano Massi
ꢆ
b
dꢇpꢆꢅꢁꢈꢇꢉꢁ ꢃꢊ Cꢀꢇꢈꢄꢋꢁꢅꢌ ꢆꢉꢂ nꢆꢉꢃcꢀꢇꢈꢄꢋꢁꢅꢌ rꢇꢋꢇꢆꢅcꢀ iꢉꢋꢁꢄꢁꢍꢁꢇ, Cꢍꢅꢁꢄꢉ uꢉꢄvꢇꢅꢋꢄꢁꢌ, Bꢇꢉꢁꢎꢇꢌ, aꢍꢋꢁꢅꢆꢎꢄꢆ; scꢀꢃꢃꢎ
c
ꢃꢊ Pꢀꢌꢋꢄcꢋ, tꢀꢇ uꢉꢄvꢇꢅꢋꢄꢁꢌ ꢃꢊ Wꢇꢋꢁꢇꢅꢉ aꢍꢋꢁꢅꢆꢎꢄꢆ, Cꢅꢆwꢎꢇꢌ, aꢍꢋꢁꢅꢆꢎꢄꢆ; Cꢀꢇꢈꢄꢋꢁꢅꢌ m310, scꢀꢃꢃꢎ ꢃꢊ Cꢀꢇꢈꢄꢋꢁꢅꢌ ꢆꢉꢂ
Bꢄꢃcꢀꢇꢈꢄꢋꢁꢅꢌ, uꢉꢄvꢇꢅꢋꢄꢁꢌ ꢃꢊ Wꢇꢋꢁꢇꢅꢉ aꢍꢋꢁꢅꢆꢎꢄꢆ, Cꢅꢆwꢎꢇꢌ, aꢍꢋꢁꢅꢆꢎꢄꢆ; Cꢇꢉꢁꢅꢇ ꢊꢃꢅ mꢄcꢅꢃꢋcꢃpꢌ, Cꢀꢆꢅꢆcꢁꢇꢅꢄꢋꢆꢁꢄꢃꢉ ꢆꢉꢂ
ꢂ
aꢉꢆꢎꢌꢋꢄꢋ, uꢉꢄvꢇꢅꢋꢄꢁꢌ ꢃꢊ Wꢇꢋꢁꢇꢅꢉ aꢍꢋꢁꢅꢆꢎꢄꢆ, Cꢅꢆwꢎꢇꢌ, aꢍꢋꢁꢅꢆꢎꢄꢆ
ABSTRACT
ARTICLE HISTORY
The preparation of discrete tetranuclear lanthanide/alkali metal (Ae)
assemblies bearing a tribenzoylmethane ligand (LH) is discussed. These
rꢇcꢇꢄvꢇꢂ 6 Jꢆꢉꢍꢆꢅꢌ 2016
accꢇpꢁꢇꢂ 23 mꢆꢅcꢀ 2016
3+
3+
assemblies have the general formula [Ln(Ae·HOEt)(L) ] , where Ln = Gd ,
4
2
KEYWORDS
lꢆꢉꢁꢀꢆꢉꢄꢂꢇꢋ; ꢈꢆgꢉꢇꢁꢄꢋꢈ;
3
+
3+
3+
+
+
+
+
Tb , Dy , Ho and Ae = Na , K , Rb . The coordination geometries of
the lanthanide species were analyzed and compared, revealing a trend
between an eight-coordinate square antiprism and triangular dodecahedron
dependent on the nature of lanthanide, alkali metal, and lattice solvent.
The potassium-containing analogs were also analyzed for their magnetic
susceptibility.
ꢁꢅꢄkꢇꢁꢃꢉꢆꢁꢇꢋ; ꢂꢄkꢇꢁꢃꢉꢆꢁꢇꢋ;
ꢆꢋꢋꢇꢈbꢎꢄꢇꢋ
1. Introduction
Coordination complexes of the trivalent lanthanide ions have been extensively investigated due to the
intrinsic magnetic and optical properties arising from the 4f-electrons. The interest is well justified by
the many technological applications found by lanthanide-containing compounds, spanning optical
displays [1–3], telecommunication devices [4, 5], magnets [6] as well as diagnostic and therapeutic
medicinal agents [7, 8]. In this field, the β-diketonate class of ligands is certainly ubiquitous, due to
CONTACT mꢆꢅk i. mꢆꢋꢋꢄꢈꢄꢎꢄꢆꢉꢃ ogꢂꢇꢉ mꢆꢋꢋꢄ
ꢈ.ꢃgꢂꢇꢉ@cꢍꢅꢁꢄꢉ.ꢇꢂꢍ.ꢆꢍ
sꢍppꢎꢇꢈꢇꢉꢁꢆꢎ ꢂꢆꢁꢆ ꢊꢃꢅ ꢁꢀꢄꢋ ꢆꢅꢁꢄcꢎꢇ cꢆꢉ bꢇ ꢆccꢇꢋꢋꢇꢂ ꢀꢁꢁp://ꢂx.ꢂꢃꢄ.ꢃꢅg/10.1080/00958972.2016.1180375.
©
2016 iꢉꢊꢃꢅꢈꢆ uK lꢄꢈꢄꢁꢇꢂ, ꢁꢅꢆꢂꢄꢉg ꢆꢋ tꢆꢌꢎꢃꢅ & fꢅꢆꢉcꢄꢋ Gꢅꢃꢍp

2
B. L. REID ET AL.
their ability to efficiently bind oxophilic trivalent lanthanide ions forming relatively stable complexes.
β-Diketonate ligands are also known to stabilize various structural motifs when binding to lanthanide
cations, ranging from mononuclear complexes to extended oxo/hydroxo clusters obtained via the
established “controlled hydrolysis”synthesis [9–12].
Given the enormous research effort on lanthanide β-diketonate complexes, it is rather surprising
that the analogous β-triketonate complexes have received scarce attention [13-15]. This is even more
remarkable considering that β-triketonate ligands are synthetically accessible via facile Claisen-type
condensations from β-diketonate ligands.
We recently initiated an investigation focused on evaluating the coordination chemistry and
optical properties of lanthanide β-triketonate complexes using the tribenzoylmethanide ligand. Our
3
+
+
studies revealed the formation of discrete Ln /Ae tetranuclear assemblies of the general formula
3
+
3+
3+
3+
+
+
+
+
[
Ln(Ae·HOEt)(L) ] , where Ln = Eu , Er , and Yb ; Ae = Na , K , and Rb [16, 17]. This family of com-
4 2
pounds proved to be remarkably robust to variations of the identity of the lanthanide as well as the
alkali metal cations. Our work was initially focused on investigation of the photophysical properties
of these assemblies, thus using red emitting Eu3+ cations and near-infrared emitting Er and Yb
3+
3+
cations. We have now continued our research effort to extend the family of these assemblies including
3
+
3+
3+
3+
the lanthanide ions Gd , Tb , Dy , and Ho . Furthermore, we have started a preliminary investi-
gation of their magnetic properties. Molecular magnets being developed around single lanthanide
nuclei with large ground spin states use the inherent magnetic anisotropy and ligand field symmetry
to produce the desired slow magnetic relaxation. More recently, dinuclear lanthanide complexes have
also been shown to exhibit desirable properties. However, unlike their mononuclear counterparts,
these complexes tend to have strong magnetic-exchange interactions through a radical bridging
atom [18, 19].
2. Results and discussion
2
.1. Synthesis
Tribenzoylmethane LH was synthesized according to our previously reported procedure [16], in which
dibenzoylmethane was reacted with benzoyl chloride and NaH in diethyl ether. The preparation of the
3
+
+
3+
3+
3+
3+
3+
+
+
Ln /Ae tetranuclear assemblies, [Ln(Ae·HOEt)(L) ] (in this case Ln = Gd , Tb , Dy , Ho ; Ae = K ,
4
2
+
Rb ), was analogous to our previously reported procedure [16, 17], whereby four equivalents of LH
and AeOH were reacted with one equivalent of hydrated LnCl in ethanol (figure 1). The synthesis of
3
the [Tb(Na·HOEt)(L) ] tetranuclear assembly is also reported herein, using NaOH. The targeted assem-
4
2
blies were in general characterized by IR spectroscopy and elemental analysis. In particular, the latter
proved in some cases difficult to obtain, as the assemblies have the tendency to co-crystallize as sol-
vates containing various degrees of lattice solvent molecules. This characteristic is analogous to the
3+
3+
3+
previously reported assemblies of Eu , Er and Yb . While the preparation of these assemblies was
Figure 1. sꢌꢉꢁꢀꢇꢁꢄc pꢆꢁꢀwꢆꢌ ꢁꢃ ꢎꢆꢉꢁꢀꢆꢉꢄꢂꢇ ꢆꢋꢋꢇꢈbꢎꢄꢇꢋ bꢇꢆꢅꢄꢉg β-ꢁꢅꢄkꢇꢁꢃꢉꢆꢁꢇ ꢎꢄgꢆꢉꢂꢋ. lꢉ3+ = Gꢂ , tb , dꢌ , hꢃ ; aꢇ = K , rb .
3+
3+
3+
3+
+
+
+

JOꢀRNAL OF COORDINATION CHEMISTRY
3
attempted with all the lanthanide ions, their isolation with elements lighter than Eu3+ has proven to
be unsuccessful to date.
2
.2. X-ray diffraction
As found previously [16, 17], the tetranuclear [Ln(Ae·HOEt)(L) ] assemblies are neutral discrete species
4
2
3
+
whereby both Ln cations are eight-coordinate by four bis-chelating β-triketonate ligands. A dimer is
formed through coordination of an alkali metal through the third keto arm of one β-triketonate mol-
ecule (see figure 2 for [Tb(K·HOEt)(L) ] structure; see Supporting Information for all other structures).
4
2
Although each of the isolated [Ln(Ae·HOEt)(L) ] assemblies are analogous in structure, it was deter-
4
2
mined that, in addition to unsolvated structures, the assemblies can also crystallize as a different solvate,
[
Ln(Ae·HOEt)(L) ] ·2(EtOH). In fact, for the [Dy(K·HOEt)(L) ] assembly, both unsolvated and solvated
4
2
4 2
structures were identified by single crystal X-ray diffraction from the same crystallization vial. This
3+
+
behavior was also previously observed for the Yb /K assembly [16, 17]. Table 1 describes each of the
assemblies presented as their crystallized species, as well as an abbreviation to describe each assembly,
{
Ln Ae }, which will be used to denote the assemblies throughout the manuscript. The assemblies are
2 2
essentially isomorphous when their structures possess the same degree of solvation, irrespective of
the identity of the lanthanide and/or alkali metal cations.
Selected distances are given in table 2 for each assembly, including average Ln-O distances and
3
+
3+
Ln⋯Ln distances. The average Ln-O distance for all assemblies decreases from Tb (~2.36 Å) to Ho
~2.33 Å), consistent with considerations based on the lanthanide contraction. The Ln⋯Ln distance in
(
each of the assemblies were affected by the lanthanide contraction, but also the presence (or absence)
of solvent molecules and the identity of the alkali metal. The lanthanide contraction gives a general
decrease in the intramolecular Ln⋯Ln distance.
Figure 2. mꢃꢎꢇcꢍꢎꢆꢅ pꢎꢃꢁ ꢃꢊ ꢁꢀꢇ [tb(K·hoeꢁ)(L) ] ꢆꢋꢋꢇꢈbꢎꢌ wꢄꢁꢀ ꢂꢄꢋpꢎꢆcꢇꢈꢇꢉꢁ ꢇꢎꢎꢄpꢋꢃꢄꢂꢋ ꢆꢁ ꢁꢀꢇ 50% pꢅꢃbꢆbꢄꢎꢄꢁꢌ ꢎꢇvꢇꢎ.
4
2
Table 1. tꢇꢁꢅꢆꢉꢍcꢎꢇꢆꢅ ꢆꢋꢋꢇꢈbꢎꢄꢇꢋ ꢋꢃꢅꢁꢇꢂ bꢌ ꢁꢀꢇꢄꢅ ꢄꢋꢃꢈꢃꢅpꢀꢃꢍꢋ cꢅꢌꢋꢁꢆꢎꢎꢄzꢇꢂ ꢋꢁꢅꢍcꢁꢍꢅꢇꢋ.
Formulation
{Ln Ae } assemblies
2
2
[
[
[
lꢉ(nꢆ·hoeꢁ)(L)4]2
{tb nꢆ }
{tb K }, {dꢌ K }, {hꢃ K }
2 2 2 2 2 2
2 2
lꢉ(K/rb·hoeꢁ)(L)4]2
lꢉ(aꢇ·hoeꢁ)(L) ] ·2eꢁoh
{tb rb }, {Gꢂ K }, {Gꢂ rb }, {dꢌ K }, {dꢌ rb }, {hꢃ rb }
4
2
2
2
2
2
2
2
2
2
2
2
2
2

4
B. L. REID ET AL.
Table 2. sꢇꢎꢇcꢁꢇꢂ ꢂꢄꢋꢁꢆꢉcꢇꢋ (Å) bꢇꢁwꢇꢇꢉ ꢁꢀꢇ ꢁwꢃ ꢎꢆꢉꢁꢀꢆꢉꢄꢂꢇ cꢆꢁꢄꢃꢉꢋ (lꢉ⋯lꢉ) wꢄꢁꢀꢄꢉ ꢁꢀꢇ ꢁꢇꢁꢅꢆꢉꢍcꢎꢇꢆꢅ ꢆꢋꢋꢇꢈbꢎꢄꢇꢋ, ꢆꢉꢂ ꢆvꢇꢅꢆgꢇ lꢉ–o
bꢃꢉꢂ ꢂꢄꢋꢁꢆꢉcꢇꢋ wꢄꢁꢀꢄꢉ ꢁꢀꢇ fiꢅꢋꢁ cꢃꢃꢅꢂꢄꢉꢆꢁꢄꢃꢉ ꢋpꢀꢇꢅꢇ. sꢁꢅꢍcꢁꢍꢅꢇꢋ ꢆꢅꢇ gꢅꢃꢍpꢇꢂ bꢌ ꢁꢀꢇꢄꢅ ꢊꢃꢅꢈꢍꢎꢆꢁꢄꢃꢉ.
Formulation
Assembly
Ln⋯Ln
Ave. Ln–O
[
[
lꢉ(nꢆ·hoeꢁ)(L)4]2
{tb nꢆ }
8.9547(4)
8.8380(5)
8.8207(4)
8.8033(2)
8.9374(1)
8.9664(5)
8.9514(5)
8.9461(4)
8.9214(2)
8.9076(4)
2.354
2.358
2.344
2.332
2.357
2.369
2.372
2.344
2.343
2.330
2
2
lꢉ(K/rb·hoeꢁ)(L)4]2
{tb K }
2 2
{
{
dꢌ K }
2 2
hꢃ K }
2
2
[
lꢉ(aꢇ·hoeꢁ)(L) ] ·2eꢁoh
{tb rb }
4
2
2 2
{
Gꢂ K }
2 2
{
{
{
{
Gꢂ rb }
dꢌ K }
2 2
2
2
dꢌ rb }
2
2
hꢃ rb }
2
2
This trend is only comparable within each formulation, and thus the position of the alkali metal–
bound ethanol has a profound effect on the packing of the tetranuclear assemblies and the Ln⋯Ln
+
+
distance. Furthermore, the presence of the K or Rb presents some anomalies in the lanthanide con-
+
+
traction trend, which is not unexpected due to the larger size of Rb compared to K .
The coordination geometries of all species were assessed using Shape Version 2.1 software [20,
2
1] and have continuous shape measures (CShM) best describing a square antiprism or a triangular
dodecahedron polyhedron (see Supporting Information for CShM values).
These CShM values were plotted on a shape map together with the CShM values of our previously
reported assemblies [17] (figure 3, for CShM values of our previously reported assemblies – see the
literature [17]). The shape map illustrates clearly that a variety of CShM clusters emerges. The presence
+
(
or absence) of the lattice solvent molecules and the identity of the Ae cation have an influence on
the specific geometry of the coordination environment around the lanthanide center. These clusters
correspond to the assemblies within the different crystallized formulations such as those described
previously.
The major factor contributing to the coordination geometry seems to be the degree of solvation and
nature of the lattice solvent molecules. The [Ln(Na·HOEt)(L) ] (I) species have a coordination geome-
4
2
try that is closest to a square antiprism, irrespective of the lanthanide cation. The deviation from the
3
+
lowest energy interconversion pathway (LEIP, black line in figure 4) increases from the smaller Yb to
3
+
the larger Eu , indicating a distortion away from the regular polyhedra with increasing lanthanide size.
From this arrangement, a slight distortion is observed for [Ln(K/Rb·HOEt)(L) ] (II) structures; however,
4
2
the coordination sphere is again best described by a square antiprism geometry. The deviation from
the LEIP follows the same trend as the [Ln(Na·HOEt)(L) ] structures which increases with increasing
4
2
lanthanide size from {Yb K } to {Tb K }.
2
2
2 2
Further distortion is evident for the previously reported [Ln(Ae·HOEt)(L) ] ·2(H O)(EtOH) (III) struc-
4
2
2
tures [17]. The deviation trend is again consistent from {Yb K } to {Er K }.
2
2
2 2
Better described as a triangular dodecahedron, the [Ln(Ae·HOEt)(L) ] ·2(EtOH) (IV) assemblies are
4
2
with two lattice ethanol molecules. Again, the deviation from the LEIP increases with increasing lan-
+
+
thanide size, from {Ho Rb } to {Eu K }. In the solvated (IV) series, the presence of K or Rb appears to
2
2
2 2
affect the deviation from regular polyhedra to a lesser extent. This observation is most likely due to the
fact that the investigated structures now include larger lanthanides, whose coordination geometry is
less affected by the size of the alkali metal.
2
.3. Static magnetic properties
+
Static magnetic properties for the K containing assemblies were investigated (figure 4). The χ T product
M
3
−1
for {Gd K } assembly decreases slightly from the room temperature value of 14.1–11.9 cm K mol at
0 K. This value is slightly lower than the expected 15.7 cm K mol spin only value for two uncoupled
Gd ions (S = 7/2, S7/2, g = 2). The susceptibility product then remains relatively constant below 20 K.
2
2
3
−1
2
8

JOꢀRNAL OF COORDINATION CHEMISTRY
5
Figure 3. tꢃp: sꢀꢆpꢇ ꢈꢆp pꢅꢇꢋꢇꢉꢁꢄꢉg ꢁꢀꢇ Csꢀm ꢃꢊ ꢁꢀꢇ 21 ꢎꢆꢉꢁꢀꢆꢉꢄꢂꢇ/ꢆꢎkꢆꢎꢄ ꢈꢇꢁꢆꢎ ꢆꢋꢋꢇꢈbꢎꢄꢇꢋ pꢅꢇꢋꢇꢉꢁꢇꢂ pꢅꢇvꢄꢃꢍꢋꢎꢌ ꢆꢉꢂ ꢀꢇꢅꢇꢄꢉ, ꢆgꢆꢄꢉꢋꢁ
ꢀꢇ ꢅꢇꢊꢇꢅꢇꢉcꢇ ꢋqꢍꢆꢅꢇ ꢆꢉꢁꢄpꢅꢄꢋꢈ ꢆꢉꢂ ꢁꢅꢄꢆꢉgꢍꢎꢆꢅ ꢂꢃꢂꢇcꢆꢀꢇꢂꢅꢃꢉ pꢃꢎꢌꢀꢇꢂꢅꢆ. tꢀꢇ bꢎꢆck ꢁꢅꢆcꢇ ꢅꢇpꢅꢇꢋꢇꢉꢁꢋ ꢁꢀꢇ ꢎꢃwꢇꢋꢁ ꢇꢉꢇꢅgꢌ ꢄꢉꢁꢇꢅcꢃꢉvꢇꢅꢋꢄꢃꢉ
ꢁ
pꢆꢁꢀwꢆꢌ (leiP) bꢇꢁwꢇꢇꢉ ꢁꢀꢇ ꢁwꢃ ꢅꢇꢊꢇꢅꢇꢉcꢇ pꢃꢎꢌꢀꢇꢂꢅꢆ. Cꢎꢆꢋꢋꢇꢋ ꢃꢊ ꢆꢋꢋꢇꢈbꢎꢄꢇꢋ ꢆꢅꢇ cꢄꢅcꢎꢇꢂ ꢆꢉꢂ ꢁꢀꢇ cꢎꢆꢋꢋ ꢉꢍꢈbꢇꢅ pꢅꢄꢉꢁꢇꢂ ꢆꢎꢃꢉgꢋꢄꢂꢇ.
Bꢃꢁꢁꢃꢈ: ꢁꢀꢇ ꢎꢇgꢇꢉꢂ ꢄꢋ ꢋꢀꢃwꢉ ꢄꢉ ꢁꢀꢇ ꢁꢆbꢎꢇ. Bꢃꢎꢂꢇꢂ ꢊꢃꢅꢈꢍꢎꢆꢁꢄꢃꢉꢋ ꢆꢅꢇ ꢅꢇpꢃꢅꢁꢇꢂ ꢄꢉ ꢁꢀꢄꢋ ꢈꢆꢉꢍꢋcꢅꢄpꢁ, wꢀꢇꢅꢇꢆꢋ ꢄꢁꢆꢎꢄcꢄzꢇꢂ ꢊꢃꢅꢈꢍꢎꢆꢁꢄꢃꢉꢋ ꢀꢆvꢇ
bꢇꢇꢉ ꢅꢇpꢃꢅꢁꢇꢂ ꢇꢎꢋꢇwꢀꢇꢅꢇ [16, 17].
3
−1
The room temperature value of χ T 28.3 cm K mol for the {Dy K } is within experimental error of the
M
2 2
3
−1
3+
6
expected values of 28.2 cm K mol for two uncoupled Dy ions (S = 5/2, L = 5, H 5/2). However χMT
1
3
−1
3
−1
for the {Tb K } (20.1 cm K mol ) and {Ho K } (21.1 cm K mol ) are lower than the expected values for
2
2
2 2
3
+
7
3
−1
3+
5
3
−1
two uncoupled Tb (S = 3, L = 3, F 23.6 cm K mol ) or Ho (S = 2, L = 4, I 28 cm K mol ) ions. As
6
15/2
temperature is lowered, χ T decreases gradually. This decrease is likely the result of depopulation of
M
the excited Stark levels and the exchange interaction between atoms [22]. At lower temperatures this
decrease is more rapid, likely the result of the crystal field effect [23] or the presence of weak antifer-
romagnetic interactions between the atoms.
The field dependence of the magnetization (figure 5) exhibits a fast increase in weak fields. When
larger fields are applied the magnetization only increases slowly for {Gd K }, {Dy K } and {Ho K }. For
2
2
2
2
2 2
{
Dy K } and {Ho K } the slow rise is likely due to the magnetic anisotropy associated with the Dy and
2 2 2 2
Ho ions. Further increasing the field results in saturation of the magnetization for both the {Gd K } and
2
2
{
Dy K }. For {Dy K } the value deviates significantly from the theoretical saturation. The magnetization
2 2 2 2

6
B. L. REID ET AL.
30
25
20
15
10
{
{
{
{
Gd2K2}
Tb2K2}
Dy2K2}
Ho2K2}
5
0
50
100
150
200
250
300
Temperature K
Figure 4. tꢀꢇ ꢁꢇꢈpꢇꢅꢆꢁꢍꢅꢇ-ꢂꢇpꢇꢉꢂꢇꢉꢁ χ t pꢅꢃfiꢎꢇꢋ ꢄꢉ ꢆ 100 oꢇ fiꢇꢎꢂ ꢊꢃꢅ ꢁꢀꢇ {Gꢂ K } (ꢅꢇꢂ), {dꢌ K } (gꢅꢇꢇꢉ), {tb K } (bꢎꢍꢇ) ꢆꢉꢂ {hꢃ K }
m
2
2
2
2
2
2
2 2
(
pꢄꢉk) ꢆꢋꢋꢇꢈbꢎꢄꢇꢋ (ꢋꢇꢇ ꢀꢁꢁp://ꢂx.ꢂꢃꢄ.ꢃꢅg/10.1080/00958972.2016.1180375 ꢊꢃꢅ cꢃꢎꢃꢅ vꢇꢅꢋꢄꢃꢉ).
continues to increase for {Tb K } and {Ho K } complexes at 7 T. The smaller than expected values meas-
2
2
2 2
ured at 7 T supports the occurrence of both magnetic anisotropy and ligand field induced splitting of
the Stark Levels [22].
3. Conclusion
3+
+
The sequence of tetranuclear Ln /Ae assemblies reported here confirms that the tribenzoylmethane
3
+
ligand can support the formation of these species for the lanthanide cations ranging from Eu to
3+
Yb , with efforts to obtain crystalline products for the lighter lanthanides being unsuccessful. The
different solvates obtained have a significant influence on the coordination sphere geometry of the
lanthanide centers, but the specific solvate obtained is not strongly influenced by the nature and size
3
+
+
of the lanthanide cations, as illustrated by the isolation of two different Dy /K solvates. The magnetic
properties of the complexes reported here are not entirely as expected, especially in considering the
values of χ T for some of the isolated assemblies. Deviations observed are tentatively ascribed to the
M
presence of various solvates, and crystal field effects, in the bulk samples.
4
. Experimental
.1. General procedures
All reagents and solvents were purchased from chemical suppliers and used as received. The ligand,
-benzoyl-1,3-diphenyl-1,3-propandione (LH), was prepared as we previously reported [16]. Hydrated
LnCl was prepared by reaction of Ln O with hydrochloric acid (5 M) [24], followed by evaporation of
4
2
3
2
3

JOꢀRNAL OF COORDINATION CHEMISTRY
7
1
5
1
0
5
{
{
{
{
Gd2K2}
Tb2K2}
Dy2K2}
Ho2K2}
0
0
1
2
3
4
5
6
7
Field (T)
Figure 5. fꢄꢇꢎꢂ-ꢂꢇpꢇꢉꢂꢇꢉꢁ m vs. h/t pꢎꢃꢁꢋ ꢆꢁ 2 K ꢊꢃꢅ ꢁꢀꢇ {Gꢂ K } (ꢅꢇꢂ), {dꢌ K } (gꢅꢇꢇꢉ), {tb K } (bꢎꢍꢇ) ꢆꢉꢂ {hꢃ K } (pꢄꢉk) ꢆꢋꢋꢇꢈbꢎꢄꢇꢋ (ꢋꢇꢇ
2
2
2
2
2
2
2 2
ꢀꢁꢁp://ꢂx.ꢂꢃꢄ.ꢃꢅg/10.1080/00958972.2016.1180375 ꢊꢃꢅ cꢃꢎꢃꢅ vꢇꢅꢋꢄꢃꢉ).
the solvent under reduced pressure. Infrared spectra (IR) were recorded on solid-state samples using
−
1
an attenuated total reflectance Perkin Elmer Spectrum 100 FT-IR from 4000 to 650 cm . Melting points
were determined using a BI Barnsted Electrothermal 9100 apparatus. Elemental analyses were obtained
at either Curtin ꢀniversity or the ꢀniversity of Tasmania.
4
.2. Magnetic measurements
Magnetization measurements were performed using a Quantum Design MPMS3 SQꢀID magnetometer.
Temperature-dependent magnetic susceptibility measurements were made on powdered polycrystal-
line samples suspended in eicosane for the {Tb K }, {Dy K }, {Ho K } and {Gd K } assemblies in an applied
2
2
2
2
2
2
2 2
field of 100 Oe from 2 to 300 K. In addition, magnetization curves in fields up to 7 T were measured
at 2 K. Results have been corrected for the diamagnetism of the sample holder, eicosane and ligand.
4
.3. General synthesis of [Ln(Ae·HOR)(L)4]2
To a mixture of LH (68–72 mg, 0.21 mmol) and hydrated LnCl (20 mg), an aqueous AeOH solution
3
+
+
+
+
(
Ae = Na , K , Rb ; 1 M, 206–218 μL, 0.21 mmol) was added. Ethanol (10 mL) was added and the mixture
heated at reflux for 30 min. The resulting mixture was hot filtered and the filtrate left to stand at RT.
Slow evaporation of the solvent over several days afforded yellow crystals (10–40 mg).
4
.3.1. [Gd(K·HOEt)(L)4]2
M.p. 269–270 °C; elemental Anal. Calcd (%) for C180H132Gd K O ·0.5(H O): C, 69.46; H, 4.31; found: C,
2
2
26
2
6
9.05; H, 4.05; ATR-IR: v = 3642 w, 3567 w, 3057 w, 3027 w, 1645 m, 1609 w, 1583 s, 1543 s, 1491 m, 1447

8
B. L. REID ET AL.
m, 1368 s, 1311 m, 1277 m, 1178 w, 1150 m, 1073 w, 1027 w, 1013 w, 999 w, 928 w, 897 m, 823 w, 780
w, 745 m, 694 m, 668 cm−1 w.
4
.3.2. [Gd(Rb·HOEt)(L)4]2
M.p. 263–264 °C; elemental Anal. Calcd (%) for C180H132Gd Rb O : C, 67.64; H, 4.16; found: C, 67.65; H,
2
2
26
3.51; the elemental analysis deviates somewhat from the theoretical values, possibly due to the presence
of multiple solvates; ATR-IR: v = 3650 w, 3571 w, 3057 w, 3021 w, 1645 m, 1610 w, 1584 s, 1543 s, 1491
m, 1448 m, 1369 s, 1311 m, 1278 m, 1179 w, 1151 m, 1074 w, 1027 w, 1013 w, 999 w, 925 w, 898 m, 823
w, 812 w, 780 w, 747 m, 694 m, 669 cm−1 w.
4
.3.3. [Tb(Na·HOEt)(L)4]2
M.p. 262–263 °C; elemental Anal. Calcd (%) for C180H132Tb Na O : C, 70.31; H, 4.33; found: C, 69.74; H,
2
2
26
4
.33; elemental analysis deviates somewhat from the theoretical values, possibly due to the presence
of multiple solvates; ATR-IR: v = 3644 w, 3557 w, 3058 w, 3032 w, 1645 m, 1584 s, 1543 s, 1491 m, 1448
m, 1369 s, 1311 m, 1278 m, 1179 w, 1150 m, 1073 w, 1027 w, 1013 w, 999 w, 974 w, 923 w, 898 m, 823
w, 780 w, 746 m, 694 m, 669 cm−1 w.
4
.3.4. [Tb(K·HOEt)(L)4]2
M.p. 239–241 °C; elemental Anal. Calcd (%) for C180H132Tb K O ·1.5(H O): C, 68.98; H, 4.34; found: C,
2
2
26
2
6
8.50; H, 3.83; elemental analysis deviates somewhat from the theoretical values, possibly due to the
presence of multiple solvates; ATR-IR: v = 3648 w, 3567 w, 3057 w, 3024 w, 1645 m, 1609 w, 1584 s, 1542
s, 1491 m, 1448 m, 1368 s, 1311 m, 1277 m, 1179 w, 1151 m, 1073 w, 1027 w, 1013 w, 999 w, 975 w, 929
-1
w, 897 m, 823 w, 780 w, 747 m, 694 m, 669 cm w.
4
.3.5. [Tb(Rb·HOEt)(L)4]2
M.p. 263–264 °C; elemental Anal. Calcd (%) for C180H132Tb Rb O ·3(H O): C, 66.44; H, 4.27; found: C,
2
2
26
2
6
6.13; H, 3.35; the elemental analysis deviates somewhat from the theoretical values, possibly due to
the presence of multiple solvates; ATR-IR: v = 3650 w, 3575 w, 3056 w, 3024 w, 1644 m, 1609 w, 1584 s,
544 s, 1491 m, 1447 m, 1369 s, 1311 m, 1276 m, 1179 w, 1153 m, 1073 w, 1027 w, 1013 w, 999 w, 925
1
-1
w, 897 m, 824 w, 780 w, 748 m, 694 m, 669 cm w.
4
.3.6. [Dy(K·HOEt)(L)4]2
M.p. 262–263 °C; elemental Anal. Calcd (%) for C180H132Dy K O : C, 69.42; H, 4.27; found: C, 69.60; H,
2
2
26
3
.78; ATR-IR: v = 3650 w, 3563 w, 3055 w, 3019 w, 2972 w, 1645 m, 1609 w, 1584 m, 1545 s, 1490 m, 1447
m, 1371 s, 1310 m, 1279 m, 1193 w, 1177 w, 1151 m, 1072 w, 1028 w, 1010 w, 975 w, 927 w, 898 m, 824
w, 780 w, 749 m, 694 m, 668 cm−1 w.
4
.3.7. [Dy(Rb·HOEt)(L)4]2
M.p. 267–268 °C; elemental Anal. Calcd (%) for C180H132Dy Rb O ·0.5(H O): C, 67.23; H, 4.17; found: C,
2
2
26
2
6
6.81; H, 3.59; the elemental analysis deviates somewhat from the theoretical values, possibly due to
the presence of multiple solvates; ATR-IR: v = 3653 w, 3571 w, 3057 w, 1645 m, 1611 w, 1584 s, 1545 s,
491 m, 1447 m, 1373 s, 1311 m, 1277 m, 1178 w, 1151 m, 1073 w, 1027 w, 1013 w, 999 w, 976 w, 925
1
−1
w, 898 m, 823 w, 812w, 780 w, 748 m, 694 m, 668 cm w.
4
.3.8. [Ho(K·HOEt)(L)4]2
M.p. 260–261 °C; elemental Anal. Calcd (%) for C180H132Ho K O : C, 69.31; H, 4.27; found: C, 69.11; H,
2
2
26
3
.87; ATR-IR: v = 3567 w, 3059 w, 3019 w, 2968 w, 1668 m, 1644 m, 1611 w, 1584 s, 1546 s, 1490 m, 1447
m, 1389 s, 1371 s, 1310 m, 1279 m, 1195 w, 1180 w, 1179 w, 1151 m, 1074 w, 1024 w, 1012 w, 999 w, 927
w, 898 m, 840 w, 823 w, 778 w, 749 m, 749 w, 694 m, 668 cm− w.
1

JOꢀRNAL OF COORDINATION CHEMISTRY
9
4
.3.9. [Ho(Rb·HOEt)(L)4]2
M.p. 268–270 °C; elemental Anal. Calcd (%) for C180H132Ho Rb O : C, 67.31; H, 4.14; found: C, 66.84; H,
2
2
26
3
.68; ATR-IR: v = 3660 w, 3570 w, 3056 w, 1645 m, 1612 w, 1584 s, 1548 s, 1492 m, 1447 m, 1373 s, 1311
m, 1278 m, 1179 w, 1151 m, 1073 w, 1027 w, 1013 w, 999 w, 976 w, 924 w, 897 m, 824 w, 780 w, 749 m,
95 m, 669 cm− w.
1
6
4
.4. X-ray crystallography
Crystallographic data for the structures were collected at 100(2) K on an Oxford Diffraction Gemini
or Xcalibur diffractometer fitted with Mo Kα or Cu Kα radiation. Following absorption corrections
2
and solution by direct methods, the structures were refined against F with full-matrix least-squares
using SHELXL-97 or SHELX-2014 [25]. ꢀnless stated below, anisotropic displacement parameters were
employed for the non-hydrogen atoms. Except for some ethanol hydrogens, all hydrogen atoms were
added at calculated positions and refined by use of a riding model with isotropic displacement parame-
ters based on those of the parent atom. CCDC-1443572 [Gd(K·HOEt)(L) ] , CCDC-1443573 [Gd(Rb·HOEt)
4
2
(
(
[
L) ] , CCDC-1443574 [Tb(Na·HOEt)(L) ] , CCDC-1443575 [Tb(K·HOEt)(L) ] , CCDC-1443576 [Tb(Rb·HOEt)
4 2 4 2 4 2
L) ] , CCDC-1443577 [Dy(K·HOEt)(L) ] , CCDC-1443578 [Dy(K·HOEt)(L) ] ∙2EtOH, CCDC-1443579
4
2
4 2
4 2
Dy(Rb·HOEt)(L) ] , CCDC-1443580 [Ho(K·HOEt)(L) ] , and CCDC-1443581 [Ho(Rb·HOEt)(L) ] contain
4
2
4 2
4 2
supplementary crystallographic data and can be obtained free of charge via http://www.ccdc.cam.ac.uk/
conts/retrieving.html, or from the Cambridge Crystallographic Data Center, 12 ꢀnion Road, Cambridge
CB2 1EZ, ꢀK; Fax: (+44) 1223-336-033; or E-mail: deposit@ccdc.cam.ac.uk.
4
.5. X-ray data refinement
4
.5.1. [Gd(K·HOEt)(L) ] ∙2EtOH
4
2
̄
Empirical formula C184H144Gd K O ; MW = 3195.68. Triclinic, space group P1, a = 13.9309(3),
b = 14.8457(3), c = 19.6249(5) Å, α = 80.167(2)°, β = 72.496(2)°, γ = 90.110(2)°, Volume = 3807.77(16) Å ,
Z = 1; ρ = 1.394 Mg m , μ = 0.993 mm , crystal size 0.53 × 0.29 × 0.21 mm ; θ
2
2
28
3
−3
−1
3
= 2.04, 34.00°.
c
min,max
Reflections collected = 120,523, unique reflections = 31,054 [R(int) = 0.0428]. Max. and min. transmis-
sion = 0.842 and 0.728. Number of parameters = 1087, S = 1.061; Final R indices [I > 2σ(I)] R1 = 0.0345,
wR2 = 0.0791; R indices (all data) R1 = 0.0419, wR2 = 0.0824; Largest diff. peak and hole 2.032 and
−3
−
1.195 eÅ . One phenyl ring and both the coordinated and uncoordinated ethanol solvent molecules
were modeled as being disordered over two sets of sites with occupancies constrained to 0.5 after trial
refinement. The coordinated ethanol OH hydrogens were not located.
4
.5.2. [Gd(Rb·HOEt)(L) ] ∙2EtOH
4 2
̄
Empirical formula C184H144Gd Rb O ; MW = 3288.42. Triclinic, space group P1, a = 14.0074(3),
b = 14.8085(4), c = 19.7192(4) Å, α = 80.083(2)°, β = 72.374(2)°, γ = 90.044(2)°, Volume = 3833.95(16) Å ,
Z = 1; ρ = 1.424 Mg m , μ = 1.563 mm , crystal size 0.31 × 0.22 × 0.16 mm ; θ
2
2
28
3
−3
−1
3
= 2.80, 31.97°.
c
min,max
Reflections collected = 47,040, unique reflections = 24,546 [R(int) = 0.0284]. Max. and min. transmis-
sion = 0.810 and 0.696. Number of parameters = 1093, S = 1.033; Final R indices [I > 2σ(I)] R1 = 0.0366,
wR2 = 0.0829; R indices (all data) R1 = 0.0453, wR2 = 0.0873; Largest diff. peak and hole 1.828 and
−3
−
1.375 eÅ . One phenyl ring and both the coordinated and uncoordinated ethanol solvent molecules
were modeled as being disordered over two sets of sites with occupancies constrained to 0.5 after trial
refinement. The ethanol OH hydrogen positions were refined with geometries restrained to ideal values.
4
.5.3. [Tb(Na·HOEt)(L)4]2
̄
Empirical formula C180H132Tb Na O ; MW = 3074.68. Triclinic, space group P1, a = 13.8911(8),
b = 14.6303(6), c = 18.0785(8) Å, α = 104.868(4)°, β = 90.597(4)°, γ = 89.885(4)°, Volume = 3550.9(3) Å ,
Z = 1; ρ = 1.438 Mg m , λ = 1.54178 Å, μ = 5.516 mm , crystal size 0.25 × 0.09 × 0.07 mm ; θ
2
2
26
3
−3
−1
3
c
min,-
=
3.13, 67.34°. Reflections collected = 34,110, unique reflections = 12,611 [R(int) = 0.0645]. Max. and
max

10
B. L. REID ET AL.
min. transmission = 0.728 and 0.389. Number of parameters = 946, S = 1.030; Final R indices [I > 2σ(I)]
R1 = 0.0519, wR2 = 0.1267; R indices (all data) R1 = 0.0629, wR2 = 0.1366; Largest diff. peak and hole
−3
2
.023 and −0.963 eÅ .
4
.5.4. [Tb(K·HOEt)(L)4]2
̄
Empirical formula C180H132K2O Tb ; MW = 3106.89. Triclinic, space group P1, a = 13.9716(3),
b = 14.5463(5), c = 18.1001(4) Å, α = 103.116(2)°, β = 89.996(2)°, γ = 89.797(2)°, Volume = 3582.59(17) Å ,
Z = 1; ρ = 1.440 Mg m , μ = 1.114 mm , crystal size 0.420 × 0.175 × 0.088 mm ; θ
26
2
3
−3
−1
3
= 2.04, 28.00°.
c
min,max
Reflections collected = 30,660, unique reflections = 17,248 [R(int) = 0.0308]. Max. and min. transmis-
sion = 0.911 and 0.700. Number of parameters = 946, S = 1.052; Final R indices [I > 2σ(I)] R1 = 0.0494,
wR2 = 0.1056; R indices (all data) R1 = 0.0628, wR2 = 0.1115; Largest diff. peak and hole 2.749 and
−3
−
1.660 eÅ . The ethanol OH hydrogen was not located.
4
.5.5. [Tb(Rb·HOEt)(L) ] ∙2EtOH
4
2
̄
Empirical formula C184H144Tb Rb O ; MW = 3243.73. Triclinic, space group P1, a = 13.9918(2),
b = 14.7907(6), c = 19.7441(3) Å, α = 80.170(1)°, β = 72.319(1)°, γ = 90.086(1)°, Volume = 3829.65(11) Å ,
Z = 1; ρ = 1.406 Mg m , μ = 1.621 mm , crystal size 0.47 × 0.44 × 0.28 mm ; θ
2
2
28
3
−3
−1
3
= 2.14, 41.15°.
c
min,max
Reflections collected = 160,326, unique reflections = 49,625 [R(int) = 0.0445]. Max. and min. transmis-
sion = 0.703 and 0.526. Number of parameters = 1081, S = 1.004; Final R indices [I > 2σ(I)] R1 = 0.0355,
wR2 = 0.0693; R indices (all data) R1 = 0.0502, wR2 = 0.0742; Largest diff. peak and hole 1.880 and
−3
−
1.056 eÅ . One phenyl ring and both the coordinated and uncoordinated ethanol solvent molecules
were modeled as being disordered over two sets of sites with occupancies constrained to 0.5 after trial
refinement. Hydrogens on ethanol oxygens were not located.
4
.5.6. [Dy(K·HOEt)(L)4]2
̄
Empirical formula C180H132Dy K O ; MW = 3114.06.Triclinic, space group P
c = 18.0746(5) Å, α = 103.049(2)°, β = 90.026(2)°, γ = 89.566(2)°, Volume = 3568.29(17) Å , Z = 1;
1
, a = 13.9658(4), b = 14.5111(4),
2
2
26
3
−
3
−1
3
ρ = 1.449 Mg m , μ = 1.174 mm , crystal size 0.24 × 0.21 × 0.10 mm ; θ
= 2.83, 30.00°. Reflections
c
min,max
collected = 85,194, unique reflections = 20,748 [R(int) = 0.0582]. Max. and min. transmission = 0.895
and 0.823. Number of parameters = 947, S = 1.157; Final R indices [I > 2σ(I)] R1 = 0.0701, wR2 = 0.1635;
−3
R indices (all data) R1 = 0.0807, wR2 = 0.1681; Largest diff. peak and hole 4.190 and −1.589 eÅ . The
ethanol OH hydrogen was not located.
4
.5.7. [Dy(K·HOEt)(L) ] ∙2EtOH
4 2
̄
Empirical formula C184H144Dy K O ; MW = 3206.19. Triclinic, space group P1, a = 13.9132(5),
b = 14.8410(8), c = 19.6256(8) Å, α = 80.221(4)°, β = 72.392(4)°, γ = 89.987(4)°, Volume = 3800.8(3) Å ,
Z = 1; ρ = 1.401 Mg m , μ = 1.105 mm , crystal size 0.21 × 0.11 × 0.04 mm ; θ
2
2
28
3
−3
−1
3
= 2.79, 27.00°.
c
min, max
Reflections collected = 27,980, unique reflections = 16,193 [R(int) = 0.0374]. Max. and min. transmis-
sion = 0.959 and 0.764. Number of parameters = 1081, S = 0.993; Final R indices [I > 2σ(I)] R1 = 0.0417,
wR2 = 0.0861; R indices (all data) R1 = 0.0529, wR2 = 0.0908; Largest diff. peak and hole 0.992 and
−3
−
1.054 eÅ . One phenyl ring and both the coordinated and uncoordinated ethanol solvent molecules
were modeled as being disordered over two sets of sites with occupancies constrained to 0.5 after trial
refinement. The ethanol OH hydrogens were not located.
4
.5.8. [Dy(Rb·HOEt)(L) ] ∙2EtOH
4 2
̄
Empirical formula C184H144Dy Rb O ; MW = 3298.93. Triclinic, space group P1, a = 13.9581(3),
b = 14.7899(3), c = 19.7191(3) Å, α = 80.097(2)°, β = 72.276(2)°, γ = 90.065(2)°, Volume = 3813.58(13) Å ,
Z = 1; ρ = 1.436 Mg m , μ = 1.681 mm , crystal size 0.28 × 0.19 × 0.11 mm ; θ
2
2
28
3
−3
−1
3
= 2.80, 35.94°.
c
min,max
Reflections collected = 113,525, unique reflections = 34,619 [R(int) = 0.0619]. Max. and min. transmis-
sion = 0.868 and 0.722. Number of parameters = 1081, S = 1.092; Final R indices [I > 2σ(I)] R1 = 0.0537,
wR2 = 0.1071; R indices (all data) R1 = 0.0703, wR2 = 0.1136; Largest diff. peak and hole 3.134 and

JOꢀRNAL OF COORDINATION CHEMISTRY
11
−3
−
1.253 eÅ . One phenyl ring and both the coordinated and uncoordinated ethanol solvent molecules
were modeled as being disordered over two sets of sites. The ethanol OH hydrogens were not located.
4
.5.9. [Ho(K·HOEt)(L)4]2
̄
Empirical formula C180H132Ho K O ; MW = 3118.92.Triclinic, space group P
c = 18.0275(4) Å, α = 102.746(2)°, β = 90.006(2)°, γ = 89.190(2)°, Volume = 3573.36(15) Å , Z = 1;
1
, a = 14.0116(4), b = 14.5056(3),
2
2
26
3
−
3
−1
3
ρ = 1.449 Mg m , μ = 1.234 mm , crystal size 0.59 × 0.43 × 0.19 mm ; θ
= 2.84, 30.00°. Reflections
c
min,max
collected = 96,102, unique reflections = 20,828 [R(int) = 0.0415]. Max. and min. transmission = 0.799
and 0.588. Number of parameters = 946, S = 1.063; Final R indices [I > 2σ(I)] R1 = 0.0354, wR2 = 0.0878;
−3
R indices (all data) R1 = 0.0392, wR2 = 0.0904; Largest diff. peak and hole 2.303 and −1.233 eÅ . The
ethanol OH hydrogen was not located with sufficient confidence to be included in the model.
4
.5.10. [Ho(Rb·HOEt)(L) ] ∙2EtOH
4 2
̄
Empirical formula C184H144Ho Rb O ; MW = 3303.79. Triclinic, space group P1, a = 13.9449(8),
b = 14.7815(6), c = 19.7069(11) Å, α = 80.013(4)°, β = 72.296(5)°, γ = 90.008(4)°, Volume = 3805.0(3) Å ,
Z = 1; ρ = 1.442 Mg m , μ = 1.743 mm , crystal size 0.21 × 0.09 × 0.045 mm ; θ
2
2
28
3
−3
−1
3
= 2.14, 28.34°.
c
min,max
Reflections collected = 28,503, unique reflections = 16,616 [R(int) = 0.0493]. Max. and min. transmis-
sion = 0.963 and 0.855. Number of parameters = 1021, S = 1.023; Final R indices [I > 2σ(I)] R1 = 0.0528,
wR2 = 0.0811; R indices (all data) R1 = 0.0767, wR2 = 0.0891; Largest diff. peak and hole 1.027 and
−3
−
0.924 eÅ . One phenyl ring, and both the coordinated and uncoordinated ethanol solvent molecules
were modeled as being disordered over two sets of sites with occupancies constrained to 0.5 after trial
refinement. Disordered atoms were refined with isotropic displacement parameters. Hydrogens on the
ethanol oxygens were not located.
Supplementary material
The Supporting Information contains molecular displacement plots of all assemblies not presented herein and raw Ln–O
distances for all crystal structures.
Acknowledgements
M.M. wishes to thank the ARC for funding (FT130100033). B.L.R. wishes to thank Curtin ꢀniversity for the Australian
Postgraduate Award. The authors acknowledge access to the facilities at the Centre for Microscopy, Characterisation and
Analysis, ꢀniversity of Western Australia.
Disclosure statement
No potential conflict of interest was reported by the authors.
Funding
This work was supported by ARC [grant number FT1301000033].
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