Crystal Growth, Characterization, and Properties of

Reduced Early Transition Metal Compounds Grown

via Hydrothermal and Molten Salt Flux Methods
Anthony J. D. Cortese, Branford Wilkins, Gregory Morrison, Jeongho Yeon, Mark D. Smith, Hans-Conrads zur Loye
Department of Chemistry and Biochemistry, University of South Carolina, Columbia, SC 29208
Abstract

NaxLn1-xMoO4 Ln = La, Nd, Sm, Eu

A limited number of compounds containing reduced early transition metals are

known due to the difficulty of their preparation. Four vanadium tartrate hybrid
materials,
A2[(VO)2(C4H4O6)(C4H2O6)(H2O)2](H2O)2
A
=
Cs,
Rb;
K2[(VO)2(C4H2O6)2(H2O)2](H2O)2; and Na2[(VO)2(C4H4O6)(C4H2O6)(H2O)7](H2O)2,
were prepared via a novel two step hydrothermal technique. Six lanthanide
molybdenum oxides, Ln5Mo2O12 Ln = Tb, Dy, Ho and Er, Ln~5Mo3O16 Ln = Nd, Sm;
four new sodium lanthanide molybdenum oxides, NaxLn1-xMoO4 Ln = La, Nd, Sm,
and Eu; a lanthanum molybdenum oxychloride, La20Mo12O63Cl4; and a barium
sodium siliconiobate, Ba3Na0.32Nb6Si4O26 were prepared via high temperature flux
methods in sealed evacuated fused silica tubes. These materials have been
characterized via powder and single crystal X-ray diffraction, UV/Vis
spectroscopy, and IR spectroscopy. Magnetism has been probed using a SQUID/
VSM magnetometer. Second harmonic generation has been investigated for
A2[(VO)2(C4H4O6)(C4H2O6)(H2O)2](H2O)2 A = Cs, Rb, K2[(VO)2(C4H2O6)2(H2O)2]
(H2O)2, La20Mo12O63Cl4, and Ba3Na0.32Nb6Si4O26.

La20Mo12O63Cl4
La20Mo12O63Cl4
S.G.
P-62m
a/
10.2241(2)
b/
10.2241(2)
c/
15.0768(4)
Z
1
R1
0.0254
wR2
0.0494

Figure 4. Temperature
dependance of the molar
magnetic susceptibility (blue),
m, and inverse susceptibility
(red), 1/m, of Na0.6Eu0.4MoO4.

Figure 3. Absorbance data for La (blue), Nd

(black), Sm (red), and Eu (green).

Figure 2 (at right). Mo1/

La1/La2/La3 oxychloride
layer viewed down the c
axis. La2 and La3 are
located on top of one
another in the c direction
and connect to Mo3 and
Mo2 layers, respectively.
Cl1 and Cl2 are located on
top of one another in the c
direction.
Figure 5. Calculated (red) and experimental
(blue) PXRD patterns for La20Mo12O63Cl4

Figure 3 (at left). Mo2/

La3/La4 oxychloride layer
viewed down the c axis.
Two La3 are located on top
of one another in the c
direction and connect to
Mo1 layers. Cl2 and Cl1 are
located on top of one
another in the c direction.

Figure 2. Calculated (red) and experimental (blue) PXRD patterns for

La (top left), Nd (top right), Sm (bottom left), and Eu (bottom right).

Ln =
S.G.
a/
c/
Z
R1
wR2

La
I41/a
5.3414(2)
11.7393(6)
4
0.0271
0.0434

Ln =
S.G.
a/
c/
Z
R1
wR2

Nd
I41/a
5.2854(2)
11.5675(6)
4
0.0185
0.0474

Ln =
S.G.
a/
c/
Z
R1
wR2

Sm
I41/a
5.2560(2)
11.4921(2)
4
0.0252
0.0664

Ln =
S.G.
a/
c/
Z
R1
wR2

Eu
I41/a
5.2797(2)
11.5869(7)
4
0.0161
Figure 1. NaxLn1-xMoO4 viewed down the a axis. Na/Ln, Mo,
0.0334
and O shown in orange, cyan, and red.

Ln5Mo2O12 Ln = Tb, Dy, Ho, Er

A2[(VO)2(C4H4O6)(C4H2O6)(H2O)2](H2O)2 A = Cs, Rb; 1, 2

K2[(VO)2(C4H2O6)2(H2O)2](H2O)2; 3

Figure 1. La20Mo12O63Cl4 viewed down the a axis. Mo1,

Mo2, Mo3, La, and Cl shown in aqua, cyan, navy, orange,
and green. Some La-O bonds omitted for clarity.
Molybdenum layers stack in A, B, A, C fashion.

Na2[(VO)2(C4H4O6)(C4H2O6)(H2O)7](H2O)2; 4
Figure 3. MoO6 1D chains showing alternating Mo - Mo distances.
Mo and O shown in cyan and red.

Figure 4. Calculated (red) and experimental (blue) PXRD patterns for Er (left) and Ho (right).

Nd4.910Mo3O16 & Sm4.952Mo3O16

Ln =
S.G.
a/
Z
R1
wR2

Figure 1. 1 and 2 viewed down the a axis. V, A, O, C, H shown in blue, yellow, red, grey,
and white. Hydrogen bonds shown as red/white stripped cylinders.

Figure 6. Absorbance data for La20Mo12O63Cl4.

Figure 4 (above). Mo3/La2/La5 oxide layer viewed

down the c axis. Two La2 are located on top of one
another in the c direction and connect to Mo1 layers.

Sm
Pn-3n
10.8934(4)
4
0.0202
0.0435

Ln =
S.G.
a/
Z
R1
wR2

Nd
Pn-3n
10.9959(7)
4
0.0205
0.0383

Figure 2. 4 viewed down the a axis. V, Na, O, C, H shown in blue, yellow, red, grey, and
white. Hydrogen bonds shown as red/white stripped cylinders.
Figure 5. Temperature dependance of the molar magnetic susceptibility
(blue), m, and inverse susceptibility (red), 1/m, of Er (left) and Ho (right).

Figure 1. Ln5Mo2O12 viewed down the c axis.

Ln, Mo, and O shown in orange, cyan, and red.

Figure 3. V2O12 dimer of 1 and 2. The dimer of 4 is similar.

V, O, C, H shown in blue, red, grey, and white.
Hydrogen bond shown as a red/white stripped cylinder.

Figure 4. V2O9 dimer of 3.

V, O, C, H shown in blue, red, grey, and white.

Figure 6. Absorbance data for Tb (black),

Dy (red), Ho (blue), and Er (green).

Figure 5. 3 viewed in the bc plane.

V, K, O, C, H shown in blue, yellow, red, grey, and white.

Ln =
S.G.
a/
b/
c/
/
Z
R1
wR2

Er
C2/m
12.1871(18)
5.7044(8)
7.4581(11)
107.884(3)
2
0.0367
0.0877

Ln =
S.G.
a/
b/
c/
/
Z
R1
wR2

Ho
C2/m
12.2959(14)
5.7377(7)
7.5300(9)
107.816(2)
2
0.0423
0.0852

Figure 7. Calculated (red) and experimental (blue) PXRD patterns for 1, 2, 3, and 4.

Figure 3. Nb3O15 trimeric columns.

Nb and O shown in cyan and red.

Figure 1. Ba3Na0.32Nb6O12(Si2O7)2 viewed down the c axis.

Ba, Na, Nb, Si, and in pink, yellow, cyan, and blue.
Na shown at full occupancy for clarity.

Figure 2. Local coordination environments of Ln~5Mo3O16.

Ln1, Ln2, Mo, and O shown in orange, purple, cyan, and red.

Figure 4. Calculated (red) and

experimental (blue) PXRD patterns for Nd.

Figure 3. Ln~5Mo3O16 viewed down the a axis. Ln1, Ln2,

Mo, and O shown in orange, purple , cyan, and red.
Ln2 - Mo bonds not shown for clarity.

Conclusions

Ba3Na0.32Nb6O12(Si2O7)2

Figure 2. Local coordination environments of Ba3Na0.32Nb6O12(Si2O7)2.

Ba, Na, Nb, Si, and O shown in pink, yellow, cyan, blue, and red.

Figure 6. Temperature
dependance of the molar
magnetic susceptibility (blue),
m, and inverse susceptibility
(red), 1/m, of Nd.

Figure 5. Absorbance data for Nd.

Figure 2. Local coordination environments of Ln5Mo2O12.

Ln, Mo, and O shown in orange, cyan, and red.

Figure 6. 3 viewed in the ab plane.

V, K, O, C, H shown in blue, yellow, red, grey, and white.

Figure1. Local coordination environments of Ln~5Mo3O16.

Ln1, Ln2, Mo, and O shown in orange, purple, cyan, and red.

Ba3Na0.32Nb6O12(Si2O7)2
S.G.
P-62m
a/
8.9998(10)
b/
8.9998(10)
c/
7.8119(17)
Z
1
R1
0.0189
wR2
0.0381

Four oxovanadium(IV) tartrates, four sodium lanthanide molybdenum(V/VI)

oxides, four lanthanide molybdenum(IV/V) oxides, one lanthanum
molybdenum(V/VI) oxychloride, one barium sodium siliconiobate(IV/V),
and two lanthanide molybdenum(V/VI) oxides have been synthesized via a
novel two step reduction technique and high temperature flux methods. Their
crystal structures were determined by single crystal X-ray diffraction.
Magnetic properties and absorbance have been determined via SQUID-VSM
and UV/Vis, respectively. Several compounds exhibit magnetic ordering.
Several compounds have absorption edges that fall in the visible region,
indicating semiconducting behavior. Conductivity measurements are
underway. SHG properties have been investigated for applicable compounds,
with several having comparable activity to a known standard.

Acknowledgments
Figure 8. Temperature dependance of the molar magnetic susceptibility (blue), m,
and inverse susceptibility (red), 1/m, of 1, 2, and 4. Temperature dependance of the
molar magnetic susceptibility (red), m, and fit (blue) of 3.

A=
S.G.
a/
b/
c/
Z
R1
wR2

Cs
P212121
8.0320(6)
10.4016(8)
23.3623(17)
4
0.0210
0.0487

A=
S.G.
a/
b/
c/
Z
R1
wR2

Rb
P212121
7.9061(8)
10.2647(11)
22.814(2)
4
0.0238
0.0543

Figure 9. Powder SHG data of 1, 2, and 3 relative to -SiO2. Absorbance data for 1
(red), 2 (green), 3(blue), and 4 (black).

A=
S.G.
a/
b/
c/
Z
R1
wR2

K
C2221
8.4341(13)
17.311(3)
25.140(4)
4
0.0339
0.0616

A=
S.G.
a/
b/
c/
Z
R1
wR2

Na
P212121
8.5931(5)
10.4332(6)
24.2289(13)
4
0.0398
0.0877

Figure 5. Temperature dependance of

the molar magnetic susceptibility (blue),
m, and inverse susceptibility (red), 1/
m, of Ba3Na0.32Nb6O12(Si2O7)2..

Figure 6. UV/Vis spectrum for

Ba3Na0.32Nb6O12(Si2O7)2.

Figure 7. IR spectrum for

Ba3Na0.32Nb6O12(Si2O7)2.

Figure 4. Calculated (red) and

experimental (blue) PXRD patterns for
Ba3Na0.32Nb6O12(Si2O7)2.

Research was supported by the U.S. Department of Energy, Office of Basic

Energy Studies, Materials Sciences and Engineering Division under DESC-0001061 and the National Science Foundation under DMR-1301757. SHG
measurements were performed at the University of Houston by T. Thao
Tran of the P. Shiv Halasyamani Group, and are gratefully acknowledged.