FINAL%

UNIVERSITY OF ZULULAND

FACULTY OF SCIENCE AND AGRICULRE

DEPARTMENT OF CHEMISTRY

MODULE TITLE INORGANIC CHEMISTRY

MODULE CODE 4CHM 312
ASSIGNMENT TOPIC Two new inorganic–organic hybrid materials based on
b- and
c-octamolybdate clusters: Synthesis, structure
determination and solid-state photochromic properties
DUE DATE 19/09/2024
LECTURER Dr Ayom

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 STUDENT NAME STUDENT NO SIGNITURE
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LECTURER REMARKS

ABSTRACT

Two new hybrid compounds, (iPr2NH2)2(NH4)2[Mo8O26] and

(C4H7N2)4[Mo8O26(C4H6N2)2] ·2H2O, synthesized at room temperature,
characterized by various techniques. Compound (1) contains b-octamolybdate,
compound (2) contains c-octamolybdate.

Introduction
Polyoxometalates (POMs) are metal-oxygen clusters made up of [MOx]n polyhedral,
with M typically a group VB or VIB metal. POMs have diverse properties useful in
medicine, biochemistry, catalysis, and more.
POMs vary in composition, size, and structure, classified as isopolyoxometalates and
Heter polyoxometalates based on their compositions. Metal element M in high oxidation
state (VV, MoVI, WVI) with oxygen atoms in coordination. The coordination of metals by
oxo ligands and the number of [MOx]n— polyhedral in a polyanion determine various
rigid and stable structural isomers. Isomerization has been observed in clusters like
Kegging, Dawson, and Lindqvist-type phases.
Nine isomers of [Mo8O26]4— octamolybdate cluster (a, b, c, d, e, f, n, g, h) are
identified. Stabilization and assembly based on number of MoO4, MoO5, MoO6 units.
Counterion choice is crucial in controlling architectures. Previous work demonstrated
stabilization of b-octamolybdate cluster with dialkylammonium counterions. Two
thermally stable compounds with [Pr2NH2] + or [(CH3)2NH2] + and [iPr2NH2]+ were
synthesized at room temperature, furthering research in this compound family. Two new
compounds, (iPr2NH2)4[Mo8O26] and (C4H7N2)4[Mo8O26(C4H6N2)2] ·2H2O, were
synthesized with b- and c-octamolybdate isomers. They were made using
diisopropylamine and 2-methylimidazole. The interest in 2-MeIm stems from its dual
character as a base (Lewis) and Bronsted (organic ligands). 2-MeIm stabilizes c-
octamolybdate isomer through protonation or complexation. iPr2NH2 stabilizes b-
octamolybdate isomer [19]. Compounds (1) and (2) synthesized at room temperature
using a non-hydrothermal method characterized by X-ray diffraction, TGA, and
spectroscopies. The study investigated solid-state photochromic properties and color-
change effects.

1. Experimental section
2.1. Materials

Malonic acid (100%), diisopropylamine (99%), 2-methylimida- zole (98%) and

ammonium heptamolybdate tetrahydrate (100%) were purchased from Sigma-Aldrich
and used without further purification. Methanol and distilled water were used as
solvent.

Synthesis

Two molybdenum-containing compounds were synthesized:

(iPr2NH2)2(NH4)2[Mo8O26] 2H2O (1) from malonic acid, diisopropylamine, and
ammonium hepta-molybdate tetrahydrate, and (C4H7N2)4[Mo8O26(C4H6N2)2] 2H2O
(2) from molybdenum trioxide, acetic acid, and 2-methylimidazole. The crystals were
obtained by evaporation and recrystallization with mass yields of 58% and 62%,
respectively. PH levels changed from 5.6 to 5.8 and 6.5 to 7.6 during the reactions.
Titanium compounds dissolved in water, stirred, and evaporated at 60°C to form a
white precipitate. Recrystallization in methanol yielded pure white XRD crystals.

Table 1
Table 1
Crystallographic data of the compounds.
Compound (i
Pr2NH2)2(NH4)2[Mo8O26]
(1)
(C4H7N2)4[Mo8O26(C4H6N2)2]
2H2O (2)
Formula
weight
(g.mol1
)
1424 1716.2
Temperature
(K)
296 293
Crystal system Monoclinic Monoclinic
Space group P21/n P21/n
a (Å) 8.0926 (2) 11.3781 (3)
b(Å) 22.4901 (7) 13.8339 (4)
c(Å) 10.1070 (3) 15.8132 (5)
b() 107.055 (3) 93.939 (3)
V (Å3
) 1758.61 (9) 2483.17 (13)
Z2 2
m(mm1
) 2.85 16.88
F(0 0 0) 21,368 1664
Crystal size
(mm3
)
0.25 0.22 0.14 0.26 0.22 0.14
R[F2 > 2r(F2
)] 0.031 0.036
wR(F2
) 0.079 0.095
2h range for
data
collection ()
3.4 to 30.5 4,3 to 71,0
hkl range 11 h 11 13 h 13
–32 k 26 16 k 16
14 l 10 19 l 18
Reflections
collected
15,914 34,462
Independent
reflections
5366 [Rint = 0.032] 4747 [Rint = 0.091]
Goodness-of-fit
on F2
1.15 1.08
Largest diff.
peak and
hole (e.A3
)
0.82/1.11 1.20/1.63

2.5. TGA measurements

Thermogravimetric and differential thermal analysis (TGA-DTA) measurement was
carried out with a Setaram Sensys Evo under an Ar mass flow rate of 20 sccm, from
room temperature to 1000 C with a heating rate of 10 C.min1. These conditions allow
studying only the thermal stability under inert atmosphere and not the degradation by
reaction at high temperature in an oxidizing medium (in air for example), which would
be more complex. The test sample of each compound was approximately 20 mg. The
return to ambient temperature (25 C) from the 1000 C at the end of the analysis was
made with a negative temperature ramp of 33 C.min

2.6. Solid-state photochromic properties

Solid-state optical properties were investigated at room temperature by Diffuse
Reflectance Spectroscopy of microcrystalline powders. Diffuse reflectance spectra
were collected on a finely ground sample with a Perkin-Elmer Lambda 1050
spectrometer equipped with a 150 mm diameter integrating sphere coated with
Spectralon, a highly reflecting fluoropolymer. Diffuse reflectance was measured from
250 to 850 nm with a 2 nm step using Spectralon as reference (100% reflectance).
The reflectance data were treated by a Kubelka-Munk transformation [28] to better
determine the absorption thresholds. The samples were irradiated with a Fisher
Bioblock labosi UV lamp (kexc = 254 nm, 6 W) at a distance of 50 mm
3. Results and discussion
3.1. Structure description and discussion
Compounds (1) and (2) have b- and c-octamolybdate isomers according to single-
crystal X-ray diffraction analysis. They crystallize in monoclinic space group system
P21/n. Compound (1) has [Mo8O26]4- anion with [NH4] + and [iPr2NH2]
+. Compound (2) includes [Mo8O26]4- cluster, [C4H7N2] +, C4H6N2, and water. The
compound consists of a octamolybdate cluster with octahedra and trigonal bipyramids
sharing corners and edges, adopting the c-[Mo8O26]4 isomer. Multiple oxygen atom
interactions occur. The bond lengths in the compounds vary, with Mo-O distances
ranging from 1.716-2.280 Å for l2-O, 1.954-2.362 Å for l3-O, and 2.155-2.439 Å for l5-
O. Comparing with compound 2, the Mo-O bond lengths differ throughout different
oxygen atoms. The longest distances are associated with l4-O or l5-O atoms, while
the shortest are with terminal oxygen atoms. The compounds display distorted
geometric structures consistent with previous studies. The c-octamolybdate isomer
contains two pentacoordinated molybdenum ions, making it an unsaturated form and
a possible reaction intermediate between a and b-octamolybdate isomers. The
metallic centers tend to be coordinated to six atoms for stability. The MoO5
bipyramidal units have vacant sites filled by nitrogen atoms, resulting in a six-
coordinated MoVI molybdenum structure. The O9-Mo4-N17 angle suggests a non-
linear skeleton, possibly due to steric hindrance from the methyl group or electronic
repulsion from neighboring oxygen atoms.

B. Sarr, A. Mbaye, Cheikh A.K. Diop et al

Fig. 1. Balls and sticks (a, c) and polyhedral (b, d) structures of the b- and c-
octamolybdate isomers.

Table 2 Types (or categories) of oxygen atoms of the b and c isomers of the
octamolybdate cluster. Types (or categories) of oxygen atoms Number of oxygen
atoms b-isomer c-isomer Ot 14 14 l2 –O 6 6 l3 –O 4 4 li –O (i = 5 for b and 4 for c) 22.
The arrangement of the oxo ligands O6, O7, O23, and O19 around the molybdenum
atom Mo4 is nearly flat, with their angular parameters totaling close to 360 degrees. In
compound (1), b-octamolybdate isomers are connected by ammonium and
diisopropylammonium cations through hydrogen bonds, forming infinite
supramolecular chains. These chains interact through various hydrogen bonds,
resulting in a 2D supramolecular structure. Compound (2) contains [Mo8O26(-L)2]4
complexes linked by hydrogen bonds and exhibits a spatial shift in the crystal
structure to reduce steric repulsions. The overall structure includes a network of
complex anions, cations, and water molecules in a three-dimensional arrangement.
 Fig. 2. Coordination of the c -octamolybdate cluster by 2-methylimidazoles
giving rise to the [Mo8O26L2]4— entity (L = 2-methylimidazole): (a) Balls and
sticks, and (b)polyhedral structures.

Fig. 3. Representation of the supramolecular interactions between

inorganic and organic entities in an infinite chain in (a) compound (1),
and (b) compound (2). For compound (2), hydrogen atoms are omitted for
clarity.

B. Sarr, A. Mbaye, Cheikh A.K. Diop et al. Polyhedron

194 (2021)

Fig. 4. Supramolecular structures of (a) compound (1), and (b) compound (2)
In compound (1), bands observed at 940, 898, 839, 708, and 661 cm—1, similar to
those in b-octamolybdate clusters. Compound (2) exhibits bands at 932, 901, 841, 677,
and 634 cm—1, suggesting lower symmetry compared to compound (1). Both
compounds show NAH stretching vibrations between 3242 and 3000 cm—1, with
additional signals in the 3500–3300 cm—1 range for compound (2).
Vibration of water molecules' OH groups indicate hydrogen bonds. 2-methylimidazole
exhibits C@C and C@N stretching vibrations. Raman spectroscopy distinguishes
[Mo8O26]4— isomers.

B. Sarr, A. Mbaye, Cheikh A.K. Diop et al.

. 3.4. Thermal analyses
Fig. 7a shows the thermogram of compound (1) with interpretation provided in Table 3.
TGA analysis reveals 35% total mass loss between room temperature and 1000 °C in
two stages. Anhydrous compound confirmed with minimal weight loss up to 260 °C.
Decomposition of inorganic b-octamolybdate anion occurs above 380 °C. Second
gradual mass loss at 380–590 °C, resulting in first degradation of b-[Mo8-O26]4. Heat
peak at 430 °C. Mixed-valence oxides Mo4O11 and Mo8O23 stable up to 607°C and
775°C respectively. Decomposition likely involves MoO3 sublimation.
Heat flow peak centered at 720°C. Agreement between experimental and calculated
mass loss of one MoO3 entity and 2.5 O2. Vapor pressure, low mass loss above 830°C.
Residue corresponds to seven MoO2 molecules, agreement with calculated value of
63%. Unique oxide presents up to 1000°C, most refractory material in Mo-O system.
Thermal decomposition of compound (1) is simpler than organic-inorganic homologs,
releasing organic part at 380°C with residue of MoO2. TGA-DTA curves in Fig. 7b show
compound (2) data. Initial 2% weight loss at 100–160 C due to H2O. Four C4H7N2+
cations released in four steps, matching calculated 19.3% loss.
Fig. 7. TGA and DTA thermograms of compounds (1) (top), and (2) (bottom). These data
are interpreted in Table 3.
Experimental weight loss corresponding to C4H6N2 entities bonded to c-[Mo8O26]
occurs in the temperature range 325–710°C, like the decomposition of the c-polyanion.
The release of the organic part of [Mo8O26(L)2] entities is not clearly distinguishable,
with a slight peak at 520°C. Mass loss between 325 and 550°C is approximately 11.5%,
confirming early decomposition.

B. Sarr, A. Mbaye, Cheikh A.K. Diop et al

Compound Experimental weight loss (%) Temperature range (°C) Heat flow peak*(°C) Released species Calculated weight loss (%)

( i Pr2NH2)2(NH4)2[Mo8O26] (1)
0.5 120–150 120 H2O traces 1.0
18.0 260–380 330 [2 (iPr2NH2) + 2 (NH4)] 17.0
6.5 380–590 430 2 O2 4,0
10.0 590–830 720 [1 MoO3 + 2.5 O2]** 15.0

(C4H7N2)4[Mo8O26(C4H6N2)2]· 2H2O (2)

2.0 100–160 150 2 H2O 2.0
2.0 160–200 185 4 C H N+ 19.3
8.0 200–260 250
2.0 260–280 275
7.0 280–325 300
31.0 325–710 520 [2 (C4H6N2)] 9.6
650 c -[Mo8O26]4— dec.*** N/A
2.0 710–880 840 1 O2 *** 1.9

) All pointed peaks are endothermic. **) Decomposition of the b-[Mo8O26] polyanion
leaving a solid residue of 65% corresponding to 7 MoO2 entities (cal. 63%). ***) Partial
decomposition of the c-polyanion leaving a black solid residue of 46%

Fig. 8. Evolution of the photogenerated absorption spectrum at room temperature under

UV irradiation (kex = 254 nm) over a period of 240 min for (a) compound (1), and (b)
compound (2)

O26]
4 in compound (2). In compound (2), the departure of 2-
methylimidazols weakens this octamolybdate anion because leaving pentacoordinated
molybdenum. This generates two types of
molybdenum in the polyanion: pentacoordinate and hexacoordiNate molybdenum. This
mixed coordination decreases the symmetry of the polyanion of compound (2) relative
to that of compound
(1) as well as its structural stability. This is probably the cause of
this difference in thermal stability

3.5. Solid-state photochromic properties

Solid-state photochromism of compounds (1) and (2) was studied using diffuse
reflectance spectroscopy in ambient conditions. Compound (1) showed intense O → Mo
charge transfer transitions in the UV region, leading to an optical band gap of ~337 nm
(3.68 eV), while compound (2) had a band gap of ~352 nm (3.52 eV). The absorption
bands of the c-[Mo8O26(C4H6N2)2] unit result from O ? Mo and N ? Mo LMCT
transitions, both lower in energy. Under UV excitation at 254 nm, compounds (1) and (2)
show photochromic responses, with compound (1) turning light brown and developing
absorption bands at 434 nm and 550 nm. Compound (2) shifts from white to pale blue
with UV exposure, showing absorption bands at 764 nm and 398 nm. Color changes in
these systems come from photoreduction of MoVI to MoV cations due to electron
transfer during UV excitation.

B. Sarr, A. Mbaye, Cheikh A.K. Diop et al

Fig. 9. Rkmax(t) vs. t plots for (a) compound (1) and (b) compound (2). The lines show
the fits of the plots according to the rate law Rkmax(t) = a/(bt + 1) + (Rkmax(0)-a).
Photochromic behavior in octahedron stabilization involves d-d transitions or
intervalence charge transfers in [MoV (OH)O5] sites. Reduced POMs show red-shifted
intervalence charge transfer bands compared to d-d transitions. Compound (1) likely
exhibits d-d transitions dominance, while compound (2) includes both d-d transitions
and electronic delocalization. N-donating ligands significantly affect octamolybdate
photoresponse. The coloration kinetics of compounds (1) and (2) were analyzed by
monitoring the change in reflectivity values over time under UV irradiation. This change
in reflectivity at the maximum absorption wavelength in the visible spectrum is linked to
the reduction in MoVI cation concentration. The data for compound (1) and compound
(2) followed a pseudo second-order kinetic law, with coloration half-life times of 62.5 and
50.7 minutes, respectively. After 180 minutes of UV exposure, the photoreduction
degree reached 78.6% for compound (1) and 81.6% for compound (2). Photochromic
hybrid POMs have a coloration rate correlated to the strength of NAH bonds. Factors
like dissociation energy and POM units must be considered. Diprotonated amino groups
may result in slow color-change effects due to low dissociation energy. Compound (2)
has a substantial hydrogen bonding network involving cations linking the oxygen POM
surface via H-bonding ineractions. The organic-inorganic interface in compound (2)
shows an increase in hydrogen bonding interactions compared to compound (1). The
photocoloration process of compound (2) is faster due to short NAH-O contacts and
hydrogen bonds with neighboring cations. Despite the hydrogen bonding network, the
slow coloration rate of compound (2) could be due to the high dissociation energy of the
NAH bond in the 2-MeIm groups.

4. Conclusion
Two new hybrid inorganic-organic materials with two isomers of the octamolybdate
anion (b and c) stabilized by organoammonium cations were successfully isolated and
characterized at room temperature. The compounds were analyzed using vibrational
spectroscopies, TGA, and single-crystal X-ray diffraction. The stabilizing entities
connect to the octamolybdate anions through hydrogen bonds to form thermally stable
2D or 3D structures. Both compounds exhibit distinct solid-state photochromic
properties, influenced by the organic cations and octamolybdate topology.

B. Sarr, A. Mbaye, Cheikh A.K. Diop et al.

materials in order to understand and rationalize their mode of formotion and to better
improve their solid-state photochromic
properties. Authors confirm no competing financial interests or personal relationships
influencing reported work.

Declaration of Competing Interest

The authors declare that they have no known competing finalcia interests or personal
relationships that could have appeared
to influence the work reported in this paper.

Acknowledgements

The authors express gratitude to various institutions in Senegal and France, including
Laboratoire de Chimie Minérale et Analytique (LA.CHI.MIA), Université Cheikh Anta
Diop de Dakar, CNRS, Université de Strasbourg, and others for financial support. All
measurements were conducted at the mentioned institutes.

Appendix A. Supplementary data

CCDC-2041975 and CCDC-1976967 provide crystallographic data. Access them for
free at http://www.ccdc.cam.ac.uk/conts/retrieving.html or contact Cambridge
Crystallographic Data Centre.

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