Inorganica Chimica Acta 525 (2021) 120471

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Research paper

Unusual redox activity of the central heteroatom manganese in Anderson

anion: Modulating its oxidation state in a gas solid reaction
Pragya Naulakha a, Neeraj Kumar Mishra a, N. Tanmaya Kumar b, Sabbani Supriya a, *
a
School of Physical Sciences, Jawaharlal Nehru University, New Delhi 110067, India
b
School of Chemistry, University of Hyderabad, Prof. C. R. Rao Road, Gachibowli, Hyderabad, Telangana 500046, India

A R T I C L E I N F O A B S T R A C T

Keywords: The orange crystalline [N(C4H9)4]3[MnIIIMo6O18{(OCH2)3CNH2}2] (1) with central Mn(III), on exposure to va­
Redox activity pors of conc. HCl is converted to green colour solid of tentative formula, [N
Gas solid reaction (C4H9)4]2[MnIIMo6O18{(OCH2)3CNH3}2] ∙ [N(C4H9)4]Cl (1red). Compound 1, on exposure to conc. HNO3 va­
Tris ligand functionalized Anderson anion
pours is converted to brown solid, which has tentatively been formulated as [MnIVMo6O18{(OCH2)3CNH3}2] ∙ 3
Central heteroatom manganese
[N(C4H9)4]NO3 (1ox). The color changes are associated with oxidation of central Mn(III) center of compound 1
into Mn(IV) in compound 1ox and reduction of central Mn(III) center of compound 1 into Mn(II) in compound
1red. Both solid state reduction and oxidation of Mn(III) center are accompanied by the protonation of amino
group of tris(hydroxymethyl) aminomethane during the gas–solid interface reactions. The conversion of com­
pound 1 into compounds 1red and 1ox in gas solid redox reactions has been characterized by various spectro­
scopic techniques, e.g., FT-IR, PXRD, EPR, DRS, 1H NMR, 13C NMR and XPS. Also, electrochemical analyses were
carried out for all the compounds.

1. Introduction of diverse central heteroatoms [36]. Tris(hydroxymethyl)methane, (RC

(CH2OH)3) ligand with different substitutions has been extensively used
The functionalization of polyoxometalates (POMs) with organic li­ for the covalent functionalization of Anderson anion [15c]. The amine
gands has widened its application in various fields, for example, nano­ substituted tris-Anderson anion [tris = (NH2–{MnMo6}–NH2)] can be
materials [1,2], photochromism [3,4], photocatalysis [5], magnetism used to functionalize the amine group post synthetically using amidation
[6], biochemistry [7–10] and macromolecular crystallography [11–14]. and aldimine condensation processes [49]. Hence post-synthetic func­
Hybrid materials include the advantages of properties of both organic tionalization strategy enables NH2–{MnMo6}–NH2 unit for further self
and inorganic components [15,16]. The synergic effects of organic assembly into variety of molecular structures. The properties of tris-
moieties on the polyoxometalates can bring about new properties, functionalized Anderson POMs can be modulated by using variety of
thereby bridging the gap between the inorganic and organic moieties counter cations [50]. Tris-functionalized Anderson compounds with
[17]. Covalent functionalization has been an important tool in the manganese as central heteroatom have been studied extensively [15c,
development of functional materials that can address the recent chal­ 15d, 50]. The properties of Anderson anion are closely associated with
lenges in the fields of the energy, catalysis and biology [18–21]. Organic central metal ion and its valence state. Tris-functionalized Anderson
modification of POM clusters evolved as one of the hottest topics of anions are isolated with varied heterocentral metal ions and oxidation
modern polyoxometalate chemistry. Various synthetic strategies, used states. Some of the central metal ions, that have been used in the tris-
for functionalization include organoimidization [22–25], organo­ functionalized Anderson anion, are Mn(III), Cr(III), Co(III), Al(III), Fe
alkoxylation [26–39], organophosphonylation, organoarsonylation (III), Ni(II), Cu(II), Zn(II) and Ga(III) [36,51–54]. The Anderson type
[40–42], organosilylation [43–45] as well as functionalization with POMs, [M(OH)6Mo6O18]n− (M = Cu2+, Zn2+, Ni2+, Cr3+, Mn3+, Al3+,
organotins [46–48]. The organoalkoxylation of Anderson anions, which Fe3+, Ga3+) functionalization by organic moiety can be single sided or
has been highly investigated, has developed a new class of poly­ double sided [51]. The organic functionalization of Anderson anion
oxometalate compounds. Their properties can be tuned by incorporation results in δ -, χ -, or ψ –isomers [36,51–52,55]. These isomers can be

* Corresponding author.
E-mail address: ssabbani@[Link] (S. Supriya).

[Link]
Received 20 September 2020; Received in revised form 15 May 2021; Accepted 21 May 2021
Available online 24 May 2021
0020-1693/© 2021 Elsevier B.V. All rights reserved.
P. Naulakha et al. Inorganica Chimica Acta 525 (2021) 120471

obtained by rearrangement of octamolybdate or by applying different prepared by HNO3 exposure to parent 1 compound, we observe redox
reaction conditions containing the organic ligand. The bridging oxygen feature for Mn4+/Mn3+ at 0.70 V vs Ag/AgCl, appearing at less anodic
atoms of Anderson anion are stronger nucleophiles than terminal oxygen region comparted to its parent compound 1, which is again due to the
atoms, therefore electrophilic alkoxy ligands preferably substitute protonation of 1ox. An oxidative response at − 0.76 V vs Ag/AgCl in the
bridging oxygen atoms over terminal oxygen atoms. Extensive in­ CV of compound 1ox (Fig. S1(c)) is due to the oxidation of nitrate anion.
vestigations have been involved in modulating the synthetic conditions Compound 1 is only soluble in CH3CN, DMF and DMSO and insoluble
to obtain various isomers of alkoxy functionalized Anderson anion in other aqueous and non-aqueous solvents. The orange color crystals of
clusters. The heteroatoms, that are stable in different oxidation states, compound 1, on exposure to HCl vapors in a gas solid reaction, are
exhibit the structural transformation as a function of change in oxidation converted to green color crystals without their dissolution (Scheme 1).
state of the central heteroatom. In the case of manganese centered tris- The resulting green color substance, obtained by exposure to HCl vapors,
Anderson anion, the oxidation state of manganese is generally found to has been found to be the reduced one (1red) with the central heteroatom
be +3. The heteroatoms, that can exhibit variable oxidation states, are as Mn(II), as characterized by various spectroscopic tools including XPS
ideal candidates to study the effect of oxidation state on the redox ac­ studies. The orange color crystals of [N(C4H9)4]3[MnIIIMo6O18
tivity of the tris-Anderson anion system. The redox activity of central {(OCH2)3CNH2}2] (1) on exposure to conc. HNO3 vapors, are trans­
heteroatom, manganese (MnIII) of tris-Anderson anion is not explored in formed to brown color solid without dissolution (Scheme 2). This brown
solid state, even though manganese can show a range of oxidation states solid is the oxidized one (1ox) with the central heteroatom as Mn(IV), as
from − 2 to +7. The synthetic attempts to isolate [MnMo6O18 found by diverse spectral characterizations including XPS studies (vide
{(OCH2)3CNH2}2]n- with Mn(II) and Mn(IV) ions as the central hetero­ infra).
atom have not been explored, despite the fact that, Anderson anion During solid to solid transformation from 1 to 1red in the gas solid
clusters with other divalent and tetravalent metal ions as central het­ reaction (compound 1 + HCl vapors), central Mn(III) of compound 1 is
eroatoms are known [51]. We have demonstrated that the crystalline reduced to Mn(II) of 1red. The possible reducing agent in this reduction
solid of compound 1 with Mn(III) central ion undergoes oxidation to Mn is chloride anion from HCl vapor. Here the anionic charge of resultant
(IV) on exposure to HNO3 vapors, and remarkably, on exposure to HCl tris Anderson anion (1red) is increased along with protonation of amine
vapors, reduced to Mn(II) in gas solid reaction. The unique gas solid groups of tris components. This situation of the cluster after reduction of
approach leads to oxidation and reduction of central metal ion which the parent compound [N(C4H9)4]3[MnIIIMo6O18{(OCH2)3CNH2}2] (1)
otherwise not obtained in in situ wet synthesis. The solid state conver­ can hypothetically be written as [MnIIMo6O18{(OCH2)3CN+H3}2]2–, that
sions of Mn(III)-Anderson into Mn(IV)-Anderson anion and Mn(II)- needs two cations for the charge balance. Since the parent compound
Anderson anion respectively are characterized by various spectro­ contains three tetrabutylammonium [N(C4H9)4]+ cations and the
scopic techniques including XPS studies and 1H NMR spectral analysis, resulting reduced compound gives positive test for the presence of
that helped us to give the tentative formulations of compounds 1ox and chloride anion (AgNO3 test), the reduced compound can tentatively be
1red. formulated as [N(C4H9)4]2[MnIIMo6O18{(OCH2)3CNH3}2] ⋅ [N(C4H9)4]
Cl (1red). The chloride anion counterbalances charge of the left out [N
2. Result and discussion (C4H9)4]+. The presence of three tetrabutyl cations in 1red is supported
by 1H NMR integration of protons of tetrabutyl ammonium cation which
The tris-functionalization of [Mn(OH)6Mo6O18]3− cluster with Mn accounts to three tratabutyl ammonium cations.
(III) heteroatom is one of the highly explored Anderson anion in this Similarly, in the case of solid to solid oxidative transformation from 1
family of covalent functionalized polyoxometalate compounds. The or­ to 1ox, the probable oxidizing agent is the nitrate anion (from nitric acid
ange color crystals of [N(C4H9)4]3[MnIIIMo6O18{(OCH2)3CNH2}2] (1), vapors). During this gas–solid reaction, Mn(III) centre of compound 1
are synthesized in a one pot reaction using [N(C4H9)4]4[α-Mo8O26], [Mn goes to Mn(IV) of compound 1ox and protonation occurs on the nitrogen
(CH3COO)3⋅2H2O] and organic ligand (OHCH2)3CNH2 in acetonitrile of two dangling –NH2 groups. Therefore in this situation, the resulting
solvent following reported procedure [52]. The oxidation state of the POM cluster would be neutral as [MnIVMo6O18{(OCH2)3CN+H3}2].
manganese heteroatom in this tris-functionalized Anderson cluster is Since there are three [N(C4H9)4]+ cations in parent compound 1 and the
+3. It is well known that manganese ion can exist in a wide range of TGA studies of the resulting oxidized compound (vide infra) shows the
oxidation states. The Anderson anions with [MnII(OH)6M6O18]4− and presence of nitrate anion, it is logical to represent the tentative formula
[MnIVM6O24]8− are reported [56], whereas the alkoxy functionalized of compound 1ox as [MnIVMo6O18{(OCH2)3CNH3}2] ∙ 3[N(C4H9)4]NO3
Anderson is known only with Mn(III) central heteroatom. Jacob, Rau, (1ox). In the resulting oxidized compound 1ox, three nitrate anions
Streb and co-workers have investigated the electrochemical properties (source: HNO3 vapor) counterbalances the positive charges of three
of compound 1 in homogenous medium [57]. The cyclic voltammogram unused [N(C4H9)4]+ cations. Again the presence of three tetrabutyl
of compound 1 in DMF solution exhibits a reversible response at 0.23 V cations in 1ox is supported by 1H NMR integration of protons of tetra­
(versus Fc+/Fc) corresponding to Mn4+/Mn3+ couple and a quasi butyl ammonium cation which accounts to three tratabutyl ammonium
reversible redox response at − 1.30 V (versus Fc+/Fc), which has been cations.
assigned to Mn3+/Mn2+ couple. The electrochemical studies of com­ The single crystal X-ray structure of compound 1 is obtained from
pound 1 clearly indicate that compound 1 has potential to undergo freshly prepared crystal, directly mounted from the relevant mother li­
oxidation and reduction at the manganese centre. We have performed quor. In dried single crystals of compound 1, the single crystallinity is
the electrochemical analyses of compounds 1, 1red and 1ox (Fig. S1 in lost. The dried crystals of compound 1 are used for redox trans­
supporting information) in DMSO solvent, using TBA.PF6 as supporting formations. Hence single crystallinity is not maintained expectedly in
electrolyte. As shown in the cyclic voltammogram (CV) plot of com­ the 1red and 1ox compounds, obtained from gas solid transformations.
pound 1 (Fig. S1(a)), an irreversible reductive response is observed at The attempts to achieve single crystals of compounds 1red and 1ox by
− 0.83 V vs Ag/AgCl indicating the reduction of Mn3+ to Mn2+ corre­ diffusion of HCl and HNO3 vapors respectively into mother liquor of
sponding to Mn3+/Mn2+ couple; the quasi-reversible red-ox response at compound 1 were not successful. Therefore redox transformations of
+98 V vs Ag/AgCl corresponds to the Mn4+/Mn3+ couple. A redox manganese ion, from compound 1 to compound 1red and compound 1 to
feature at − 0.99 V vs Ag/AgCl corresponding to Mn3+/Mn2+ couple is compound 1ox, have been characterized by various techniques. The solid
observed in the CV of compound 1red (Fig. S1(b)); this feature of Mn3+/ state redox transformations carried out by alternate oxidizing and
Mn2+ couple has appeared at more cathodic region comparted to that of reducing agent did not give desired products. Addition of H2O2 to single
its parent compound, because 1red is in protonated form due to HCl crystals of compound 1 (not soluble in H2O2) did not show any color
exposure. On the other hand, in the CV of compound 1ox (Fig. S1(c)), change. The stability of Anderson anion cluster during gas solid redox

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Scheme 1. The solid-state reduction of tris-functionalized Anderson polyoxometalate: reduction of central heteroatom manganese in a gas solid reaction from Mn
(III) (1) to Mn(II) (1red).

Scheme 2. The solid-state oxidation of tris-functionalized Anderson polyoxometalate: oxidation of central heteroatom manganese in a gas solid reaction from Mn(III)
(1) to Mn(IV) (1ox).

transformations is established by diverse studies.

2.1. Fourier-Transform infrared (FT-IR) studies

Infrared spectroscopy is one of the useful tools for characterization of

various polyoxometalate compounds. The FT-IR spectrum of compound
1red (Fig. 1b)) is comparable to the spectrum of parent compound 1
(Fig. 1a)) along with appearance of new peaks. The band at 1040 cm− 1
corresponds to the C–O stretching vibration of tris ligand. The peaks for
Mo-O stretching vibrations appear in the region 900–950 cm− 1; Mo=O
stretching vibrations appear around 850–900 cm− 1 and Mo-O-Mo
stretching vibrations are observed around 400–500 cm− 1. The C–H
stretching vibrations are seen in the range of 2500–2900 cm− 1. The
protonation of tris-amine group (by HCl vapor) in reduced compound is
represented by appearance of a broad feature at 3400 cm− 1 along with
other new peaks in the range of 1500–1600 cm− 1 and 1100 cm− 1,
characteristic to N–H and C–N stretching frequencies of tris-
ammonium cation. The structural stability of Anderson anion in 1red is
indicated by maintenance of metal-oxo IR bands in the range of 1100 to
500 cm− 1 (Fig. 1b)).
Fig. 1. The FT-IR spectra of (a) parent compound 1, (b) reduced compound
The FTIR spectrum of [MnIVMo6O18{(OCH2)3CNH3}2] ∙ 3[N
1red obtained on exposure of crystals of compound 1 to conc. HCl vapors and (c)
(C4H9)4]NO3 (1ox) (Fig. 1c)) shows the extra bands in comparison to the
oxidized compound 1ox obtained on exposure of crystals of compound 1 to
IR spectrum of compound 1 (Fig. 1a)). The additional bands due to conc. HNO3 vapors. The peak around 2300 cm− 1 is due to background CO2 in
protonation of tris-amine groups is represented by the broad feature at compound 1.
around 3200 cm− 1; the medium feature in the range of 1600–1500 cm− 1
correspond to the N–H bond and C–N stretching corresponds to 1020
compound 1ox (Fig. 1c)). During the gas solid interaction, there will
cm− 1. The protonation of tris amine and oxidation of manganese central
always be adsorbed nitrate groups and removal of adsorbed nitrate by
atom lead to the incorporation of nitrate anions. The characteristic ni­
washing with the polar solvents leads to the regeneration of original
trate peak around ~ 1400 cm− 1 can be observed in the IR spectrum of

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compound (brown to orange). Hence number of nitrate anions incor­

porated into the system could not be quantified.

2.2. Powder X-ray diffraction (PXRD) analysis

The single crystal X-ray diffraction of compounds 1red and 1ox was
not possible. Therefore the compounds 1red and 1ox were characterized
by powder X-ray diffraction (PXRD) studies. The crystalline nature of
green solid 1red is shown in its PXRD plot (Fig. 2b). The comparison of
PXRD pattern of compound 1red to that of parent compound 1 (Fig. 2a))
shows the phase transition. Thus, the solid state transition of compound
1 to 1red leads to change in crystal packing.
Exposure of crystalline compound 1 to HNO3 vapor in gas solid re­
action is converted to compound 1ox solid with the incorporation of
nitrate anion into the crystal lattice of compound 1. The inclusion of
bulkier nitrate anions into the crystalline 1 results in loss of crystallinity
in compound 1ox as shown in Fig. 2c).
Fig. 3. The EPR spectrum of the reduced compound 1red, obtained by the
exposure of parent compound 1 to conc. HCl vapors.
2.3. Electron paramagnetic resonance (EPR) spectroscopic analysis

The orange color crystals of [N(C4H9)4]3[MnIIIMo6O18

{(OCH2)3CNH2}2] (1) on exposure to conc. HCl vapors are converted
into [N(C4H9)4]2[MnIIMo6O18{(OCH2)3CNH3}2] ∙ [N(C4H9)4]Cl (1red)
in which central heteroatom Mn(III) is reduced to Mn(II). The formation
of Mn(II) in compound 1red is studied by EPR spectroscopy. The EPR
spectrum of the compound 1red solid, recorded at room temperature, is
shown in Fig. 3. The EPR spectrum of 1red demonstrates six lines spec­
trum with hyperfine splitting due to 55Mn with I = 5/2 with corre­
sponding g-values of 2.119, 2.076, 2.030, 1.986, 1.935 and 1.889. The
six lines EPR of 1red is characteristic of the Mn(II), thereby corroborating
the reduction of Mn(III) to Mn(II) in a gas solid transformation. The
redox conversion of Mn(III) to Mn(II) is further studied by XPS and NMR
spectroscopy (vide infra). The relevant experimental details for the solid
state conversion are given in the experimental section. The EPR spec­
trum of brown solid [MnIVMo6O18{(OCH2)3CNH3}2] ∙ 3[N(C4H9)4]NO3
(1ox), obtained from compound 1 in a redox transformation, is recorded
at room temperature. The oxidation of Mn(III) to Mn(IV) is supported by
the EPR signals at g-values of 1.995 and 3.8, characteristic to Mn(IV) as
shown in Fig. 4.
Fig. 4. The EPR spectrum of the oxidized compound 1ox, obtained by the
exposure of parent compound 1 to conc. HNO3 vapors.

2.4. Nuclear magnetic resonance (NMR) spectroscopic analysis

The recent studies on various alkoxy functionalized Anderson com­

pounds show that the reaction condition plays an important role in the
isolation of various isomers. The coordination of alkoxy group to
bridging oxygen (μ2-O or μ3-O) sites can be decided by modulation of
central metal ion oxidation state. The structural transformations in
alkoxy functionalized Anderson cluster are associated with coordination
of alkoxy ligand to μ2-O or μ3-O atoms of Anderson anion. These struc­
tural transformations are dependent on substitutions on the alkoxy
group and reaction condition. The single crystal X-ray structure of
compound 1 shows that six μ3-O sites are functionalized by two tris
groups leading to double sided δ/δ isomer. A particular functionalization
and the resulting structural isomer of the compound 1red have been
investigated by the 1H and 13C NMR spectral studies. Due to the presence
of paramagnetic manganese center in the compounds 1red and 1ox, it
results in line broadening ofthe signals in corresponding 1H NMR spectra
that is consistent with the 1H NMR spectra reported for compound 1.
Fig. 2. The PXRD patterns of (a) parent compound 1, (b) reduced compound Another distinct feature is the signals of the CH2 groups that experience
1red obtained on exposure of crystals of compound 1 to conc. HCl vapors and (c) a pronounced paramagnetic downfield shift and appear as a broad signal
oxidized compound 1ox obtained on exposure of crystals of compound 1 to at δ 65 ppm [36].
conc. HNO3 vapors. The 13C NMR characterization technique is one of the effective

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methods to differentiate δ isomer from χ isomer. The chemical shift of signify the structural integrity of the system even after solid state redox
carbon, bonded to μ2-O, is higher than that of the carbon, bonded to μ3-O conversion. [N(C4H9)4]3[MnIIIMo6O18{(OCH2)3CNH2}2] (1) possess
atoms. Therefore δ isomer possesses single type of CH2 tris-ligand car­ two (OCH2)3CNH2 (tris) ligands on either side of Anderson cluster.
bons that are coordinated to μ3-O. On the other hand, χ isomer consists When compound 1 is exposed to HCl vapors, Mn(III) is reduced to Mn(II)
of two types of CH2 tris-ligand carbons: one that are coordinated to μ3-O and the two amine groups of the tris-ligand are protonated resulting in
and other that are coordinated to μ2-O atoms. The 13C NMR spectrum of tris-ammonium cations, present on both sides of the Anderson anion.
compound 1 in d6-DMSOshows tetrabutylammonium carbons (four The appearance of two types of peaks at chemical shifts 10 ppm and 7.5
types of carbons) group with chemical shifts of 13.61 ppm, 19.30 ppm, ppm corresponding to the protons of tris-ammonium cation ascertains
23.06 ppm and 57.50 ppm and tris ligand carbons (methylene carbon that two tris-ammonium cations are not equivalents. We assume that the
and tertiary carbon). The presence of one type of chemical shift corre­ hydrogen bonding environment of the two tris-ammonium cations are
sponding to methylene groups (tris ligand) in 13C NMR spectra of different, which is translated into the two chemical shift positions. The
compounds 1red and 1ox implies δ/δ conformation. Hence it indicates proton NMR spectrum of 1ox (Fig. 6 (b)) is similar to that of 1red, both
that δ/δ conformation is retained in the 1red and 1ox compounds even showing the presence of tetrabutyl ammonium cation protons as well as
after solid to solid redox conversions (Fig. 5). tris ammonium cationic group resulted from protonation of amine
The proton NMR spectrum of 1red compound, obtained by exposure groups of tris ligand during solid state conversions from compound 1 to
of compound 1 to HCl vapors in d6-DMSO solution (Fig. 6 (a)) shows the 1red and 1ox.
shift of amine proton to low field due to the protonation of amine of tris- The presence of protons of tetrabutyl ammonium cation in 1red and
ligand. Other peaks positions, that are similar to those of compound 1, 1ox is confirmed by the appearance of peaks in the 1H NMR spectra of

Fig. 5. (a) The 13C NMR spectrum of the reduced compound (1red) obtained by the exposure of parent compound 1 to conc. HCl vapors. (b) The 13C NMR spectrum of
the compound (1ox) obtained by the exposure of compound 1 to conc. HNO3 vapors.

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Fig. 6. (a) The 1H NMR spectra of the reduced compound (1red) obtained by the exposure of parent compound 1 to conc. HCl vapors and (b) the 1H NMR spectra of
the oxidized compound (1ox) obtained by the exposure of compound 1 to conc. HNO3 vapors.

compounds 1red and 1ox at 0.93 ppm, 1.31 ppm, 1.56 ppm and 3.15 ppm Mn(III) to Mn(IV) on exposure of compound 1 to HNO3 vapors is evident
(see Fig. 6 (a) and 6(b)). We have proposed the tentative formulae of by binding energies at ~ 642 eV (2p3/2) and ~ 648 eV (2p1/2) as
compounds 1red and 1ox based on the 1H NMR integration of protons depicted in Fig. 9. Thus the formations of Mn(II) metal ion in 1red and
corresponding to tetrabutyl ammonium cation which accounts to three Mn(IV) in 1ox are corroborated by XPS studies. The oxidation state of
tratabutyl ammonium cations 1red and three tratabutyl ammonium molybdenum ion (as MoVI) in compound 1red is confirmed by Mo(VI)
cations in 1ox as shown in Fig. 6(a) and 6(b). 3d5/2 (~228 eV, ~ 229 eV, ~ 231 eV) and Mo(VI) 3d3/2 (~232 eV, ~
235 eV) binding energies as shown in Fig. 7. The oxidation state of
2.5. X-ray photoelectron spectroscopic (XPS) analysis molybdenum ion (as MoVI) in compound 1ox is confirmed by Mo(VI)
3d5/2 (~227 eV, ~ 228 eV, ~ 229 eV) and Mo(VI) 3d3/2 (~231 eV, ~
The X-ray photoelectron spectroscopy (XPS) data for 1red and 1ox 234 eV) as shown in Fig. 11. The formation of ammonium cationic
were obtained by using Al Kα X-ray source of energy 1486.7 eV on centres in compounds 1red and 1ox is reflected in their corresponding
Omicron electron spectroscopy for chemical analysis (ESCA) (Oxford nitrogen XPS spectra (Fig. 8 and Fig. 10 respectively) with N(1s) of
Instrument Germany). The XPS spectra corresponding to manganese primary amine (~395 eV), N(1 s) of protonated amine (~398 eV). The
metal ion show the presence of both Mn(II) 2p3/2 (~641 eV) and Mn(III) nitrogen XPS spectrum of compound 1ox additionally shows the binding
2p3/2 (~643 eV) indicating reduction of Mn(III) to Mn(II) (Fig. 7). energy related to nitrate anion N(1 s) at > 402 eV. Fig. S3 (SI) dem­
Presence of Mn(III) in the resulting 1red cannot be avoided because the onstrates the oxygen XPS spectra in compound 1red and 1ox, respec­
conversion of 1 into 1red was carried out by the exposure of compound 1 tively. The presence of C–C and C–N carbon atoms in compounds 1red
to HCl vapors in the solid state in vapour-solid reaction. The oxidation of and 1ox can be understood from the XPS spectra, given in Fig. S4 (SI).

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Fig. 7. Left: XPS plot showing that Mn(II) (~641 eV) and Mn(III) (~643 eV) are present in reduced compound obtained on exposure of parent compound 1 to conc.
HCl vapors; Right: XPS plot showing Mo(VI) 3d5/2 (~228 eV, ~ 229 eV, ~ 231 eV, ~ 232 eV, ~ 235 eV) present in reduced compound 1red.

compounds 1 and 1red are comparable, where as in compound 1ox, a

weight loss of approximately 18% is observed in the temperature range
of ~ 121–127 ◦ C which can be due to loss of one tetrabutylammonium
nitrate along with one ammonium nitrate group.

2.6. Diffuse reflectance spectral (DRS) analysis

The electronic absorption (diffuse reflectance) spectra of parent 1,

reduced compound 1red and oxidized compound 1ox have been recorded
in their solid state. As shown in Fig. 11, all three compounds show a
broad feature at 300–600 nm. This broad feature is due to the ligand to
metal (O → Mn+) charge transfer transition. Generally, Mn(II) coordi­
nation complexes show weak d-d transitions around 500–550 nm; but in
the present Mn(II) compound 1red, the weak d-d band has been masked
by the intense LMCT transition. In the case of oxidized compound 1ox, a
shoulder around 450 nm can be assigned to oxygen to MnIV charge
transfer transition. Other reported Mn(IV) mononuclear complexes also
show a similar ligand to metal charge transfer transition in this region
[58].

3. Conclusions
Fig. 8. XPS plot showing that N (1s) of primary amine (~395 eV) and N (1s) of
protonated amine (~398 eV) are present in reduced compound 1red. The solid state redox conversions of Anderson anions are scarcely
reported in the literature. The covalent functionalization of poly­
The thermogravimetric analyses (TGA) of compounds 1, 1red and 1ox oxometalate shows synergistic effect on the redox properties of cluster
are given in Fig. S5, Fig. S6 and Fig. S7 respectively (SI). The weight anion. In many of the heteropolyoxometalate clusters, the redox activity
losses in the range of 262 ◦ C to 290 ◦ C in all the compounds indicate the of addenda atoms is explored extensively. Recently the redox activity of
complete loss of organic component (TRIS). The TGA analysis of central metal ions of heteropoly anions is investigated and these studies

Fig. 9. XPS plots showing Mn(III) (~640 eV, ~ 651 eV) and Mn(IV) (~642 eV, ~ 648 eV) are present in oxidized compound 1ox.

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Fig. 10. Left: XPS plot showing that Mo(VI) 3d5/2 (~227 eV, ~ 228 eV, ~ 229 eV, ~ 231 eV, ~ 234 eV) is present in oxidized compound 1ox; Right: XPS plot
showing N(1s) of primary amine (~395 eV), N(1 s) of protonated amine (~398 eV) and N(1s) of nitrate anion (>402 eV) in oxidized compound 1ox.

manganese anion systems with appropriate substitutions have potential

to be reversible. These redox conversions, in the present work, have
been characterized by electrochemical analyses and various spectro­
scopic techniques, such as, IR, PXRD, EPR, DRS, 1H NMR, 13C NMR and
XPS, spectral techniques.

4. Experimental section

4.1. General

All the chemicals were of reagent grade, used as received from the
commercial sources for the syntheses (sodium molybdate dihydrate,
tetrabutylammonium bromide, manganese acetate dihydrate, tris
(hydroxymethyl) aminomethane, deionized water, conc. hydrochloric
acid, conc. nitric acid, ethanol, acetone, diethyl ether and acetonitrile).
The precursor [N(C4H9)4]4[α-Mo8O26] has been synthesized following
the reported procedure [52].
The Fourier transform infrared spectral studies of the solid com­
pounds 1, 1red and 1ox were recorded in the range of 400–4000 cm− 1 at
room temperature using an IRAffinity-1S Shimadzu FT–IR spectropho­
tometer. The samples were analyzed in the ATR (attenuated total
reflection) mode. Prior to the analysis, a background scan of air was
collected. All the solid samples were analyzed by powder X-Ray
diffraction technique using CuKα1 radiation (1.54 Å) in the range 3˚- 45˚
Fig. 11. Diffuse reflectance spectra of (a) the parent compound 1, (b) reduced
compound 1red obtained on exposure of parent 1 crystals to conc. HCl vapors at the rate of 4˚min− 1 carried on a Rigaku X-ray Powder Diffractometer
and (c) oxidized compound 1ox obtained by the exposure of parent compound 1 Miniflex-600 operating in Bragg-Brentano geometry. The sample was
to conc. HNO3 vapors. prepared by layering a fine powder of the solid samples on the surface of
a glass sample holder. The electron paramagnetic resonance (EPR)
have led to interesting structural and chemical properties [59]. Here in studies of all the compounds were recorded at room temperature in a
this paper, we have demonstrated the redox flexibility of central man­ fixed frequency mode (X-band spectroscope) using a Bruker Model EMX
ganese ions in an organically functionalized Anderson anion towards MicroX. The nuclear magnetic resonance (NMR) studies of the com­
oxidation as well as reduction in unique gas–solid conversions. The pounds 1, 1red and 1ox were recorded on a Bruker Avance III (500 MHz)
crystalline solid of Mn(III) present in the parent cluster anion undergoes in d6-DMSO solvent. TMS was used as the internal solvent and the
reduction on exposure to HCl vapor without destruction of the system in chemical shifts are indicated as δ values with respect to TMS. The solid
gas solid reaction. Interestingly, the parent compound 1 on exposure to samples 1, 1red and 1ox were analyzed by the diffused reflectance
HNO3 acid vapors undergo oxidation of the central heteroatom center, i. spectroscopy (DRS) experiments carried out in the wavelength range
e., Mn(III) to Mn(IV) retaining the overall system intact. The attempts to 220–1400 nm on a Shimadzu UV 2600 UV–vis spectrophotometer.
isolate reduced and oxidized compounds through in situ direct synthesis Before the sample analysis is done, the baseline is recorded using a
were not successful. The present system has two terminal –NH2 func­ sample holder filled with barium sulphate as a reference. For the sample
tionalities per POM cluster anion, each having lone pair of electrons and preparation, the top of the sample holder containing BaSO4 is layered
are protonated during solid state redox conversions. This protonation with the solid sample. The X-ray photoelectron spectroscopy (XPS) data
influences the redox properties of the system leading to conversions of for compounds 1red and 1ox were obtained using Al Kα X-ray source of
Mn(III) center toward oxidation (by HNO3 vapor) to Mn(IV) as well as energy 1486.7 eV on Omicron electron spectroscopy for chemical
reduction (by HCl vapor) to Mn(II). This work has focused on a unique analysis (ESCA) (Oxford Instrument Germany). The thermogravimetric
solid state red-ox conversion in polyoxometalate chemistry in general, analysis (TGA) of all the compounds were carried out on a Mettler
that has not been explored before. We believe that tris functionalized Toledo TGA 1 instrument in the temperature range of 25◦ -800 ◦ C at the

8
P. Naulakha et al. Inorganica Chimica Acta 525 (2021) 120471

rate of 5 ◦ C min− 1 under an inert flow of dry nitrogen gas (flow rate: 20 Writing - original draft, Writing - review and editing. Neeraj Kumar
cm3min− 1). A blank is run prior to recording of data of the samples Mishra: Software. N. Tanmaya Kumar: Investigation, Methodology.
under the same conditions using an empty crucible. The electrochemical Sabbani Supriya: Supervision, Conceptualization, Investigation, Re­
studies of all the compounds 1, 1red and 1ox in DMSO solvent were sources, Data curation, Writing - original draft, Writing - review and
recorded using a Zahner Zanium electrochemical work station operated editing.
with Thales software. A three-electrode electrochemical cell consisting
of glassy carbon (GC) as working electrode, Ag/AgCl (1 M) as the Declaration of Competing Interest
reference electrode, and Pt-flag as counter electrode in TBA.PF6 solution
as supporting electrolyte. The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
4.2. Synthesis of [N(C4H9)4]3[Mn(III)Mo6O18{(OCH2)3CNH2}2] (1) the work reported in this paper.

The parent compound 1 was synthesized in a one pot reaction Acknowledgements

following the standard procedure as mentioned in the literature [52]. A
mixture of [N(C4H9)4]4[α-Mo8O26] (8 g, 3.7 mmol), [Mn We thank SERB, DST, Government of India with project number (SB/
(CH3COO)3⋅2H2O] (1.49 g, 5.6 mmol) and (CH2OH)3CNH2 (1.56 g, 12.8 EMEQ-090/2014) for the financial support. The financial grant from
mmol) in 150 ml acetonitrile solvent was refluxed for 17 h at 84–88 ◦ C. UPE-II (project No. 58), DST-PURSE and DST-FIST are gratefully
The orange solution was cooled down to RT and filtered to remove a acknowledged. PN thanks UGC-BSR for fellowship. We thank AIRF, an
brown solid. The filtrate was kept for ether diffusion for 2 h at RT. It gave instrumentation facility at JNU. We acknowledge Materials Research
white precipitate. It was then filtered and kept for ether diffusion again. Centre at Malaviya National Institute of Technology, Jaipur for XPS
The thick orange crystals were obtained on the walls of the beaker. The facility. Authors acknowledge Nasir Ali and Jeetendra Tiwari for their
obtained crystals were filtered and washed with acetonitrile followed by help in analyzing XPS data.
diethyl ether. (Yield 7.28 g, 80%). IR (cm− 1): 3500 (N–H stretch, w),
2966.67 (C–H stretch, s), 2932 (C–H stretch, s), 2873.03 (C–H Appendix A. Supplementary data
stretch, m), 1481.6 (C–H stretch, s), 1462.93 (C–H stretch, m),
1378.67 (C–H stretch, s), 1036.53 (C–O stretch, s), 942.93 (Mo-O Supplementary data to this article can be found online at [Link]
stretch, s), 929.3 (Mo-O stretch, s), 898.13 (Mo = O stretch, m), 678.9 org/10.1016/[Link].2021.120471.
(Mo-O-Mo stretch,s), 559.73 (Mo-O-Mo stretch, s), 459.2 (Mo-O-Mo
stretch, s), 414 (Mo-O-Mo stretch, s). 1H NMR (500 MHz, DMSO): δ 0.93 References
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