Cuboctahedral [In36(μ-OH)24(NO3)8(Imtb)24]MOF with Atypical Pyramidal Nitrate Ion in SBU: Lewis Acid-Base Assisted Catalysis and Nanomolar Sensing of Picric Acid

Article abstract of DOI:10.1021/acs.inorgchem.1c00981

A robust and multifunctional cuboctahedral [In36(μ-OH)24(NO3)8(Imtb)24] MOF (In(Imtb)-MOF) with an atypical pyramidal nitrate ion-containing hitherto unknown SBU core [In9(μ-OH)6(NO3)] is reported. The intra- and interlayer nitrate ions adopt pyramidal an

Full text of DOI:10.1021/acs.inorgchem.1c00981

pubs.acs.org/IC
Communication
Cuboctahedral [In (μ-OH) (NO ) (Imtb) ]MOF with Atypical
36
24
3 8
24
Pyramidal Nitrate Ion in SBU: Lewis Acid−Base Assisted Catalysis
and Nanomolar Sensing of Picric Acid
Sharad Kumar Sachan and Ganapathi Anantharaman*
Cite This: Inorg. Chem. 2021, 60, 9238−9242
Read Online
ACCESS
Metrics & More
Article Recommendations
*
sı Supporting Information
ABSTRACT: A robust and multifunctional cuboctahedral [In (μ-OH) (NO ) (Imtb) ] MOF (In(Imtb)-MOF) with an atypical
3
6
24
3 8
24
pyramidal nitrate ion-containing hitherto unknown SBU core [In (μ-OH) (NO )] is reported. The intra- and interlayer nitrate ions
9
6
3
adopt pyramidal and inverted pyramidal shapes, which separates the active indium site [(In (μ-OH) )NO -(In (μ-OH) )] and
3
2
3
3
2
linear In (μ-OH) by 0.5 and 0.9 nm, respectively. Additionally, the high density of active metal sites shows remarkable catalytic
3
2
activity with higher TOF even for sterically hindered substrates in Strecker synthesis and CO cycloaddition. Moreover, the
2
luminescence behavior of In(Imtb)-MOF and the presence of uncoordinated nitrogen atoms are exploited for selective sensing of
explosive trinitrophenol (TNP) with a detection limit (LOD) of 2.3 ppb.
he advent of the discovery of the underlying principles
(topologies) to create precise networks such as the node-
indium organic framework (InOF) are observed (Chart
3
4−36
T
1).
To incorporate luminescence in the MOF, we
spacer, isoreticular chemistry, and the molecular building block
approach played a significant role in the preparation of metal−
organic frameworks (MOFs) in nano dimensions. Further, the
availability of a spectrum of metal ion geometry and linker
designs has propelled the area of porous coordination
Chart 1. SBUs from Indium Monomer
1
−16
polymers (PCPs) and MOFs in the past three decades.
Modulations of linkers, from simple multicarboxylic acids to
functional N-/O-donor or heterocyclic groups containing
organocarboxylic acids, have shown a tremendous increase in
gas adsorption and Lewis base assisted organic transformations
1
3,17−19
(Chart S1).
Similarly, there has been a sustained
interest in the quest for secondary building units (SBUs) of
metal ion clusters made of metal oxo/hydroxo units. The
structural rigidity of the hydrolyzed SBUs contributes
immensely to the framework stability under different chemical
environments and provides Lewis acid sites (metal centers) in
2
0−22
prepared the linker, 2,4,5-tris(4-carboxy-phenyl)-1-methyl
the pores.
Moreover, combined Lewis acidic and basic
37−39
imidazole (H Imtb), a derivative of lophine.
Herein, we
3
sites could make the resultant MOFs truly multifunctional, and
therefore a single MOF can be utilized for multiple
report the thermally and hydrolytically stable nanoporous
InOF having a uniform cuboctahedral [In36(μ-
OH) (NO ) (Imtb) ] cage. The SBU comprises pyramidal
2
3−25
applications.
If the MOFs are luminescent, then the
2
4
3 8
24
adsorption or reaction occurring at the MOFs surface can be
monitored.
−
NO3 ions bridged between In (μ-OH) units like 3.111 in
3
2
40
organophosphonates (Chart S2). Thus, the well-separated
and highly dense Lewis acidic and basic centers manifest the
catalytic activity in Strecker synthesis and cyclic organo-
The sol−gel route is preferable for introducing metal
oxo(hydroxo) clusters in SBUs of MOFs; however, the
coordination between water/anions to the metal center-
26−28
carbonate preparation using CO . Moreover, the free nitrogen
2
compete with each other in an aqueous solution.
A
systematic evaluation of hydrolysis of group 13 M(NO3)3
Received: March 30, 2021
Published: June 11, 2021
indicates incomplete hydrolysis keeping the In-ONO bond
2
2
9
intact. This is advantageous to preparing well-separated and
highly dense metal centers for catalytic activity. Further, the
addition of modulators controls such a coordination environ-
3
0−33
ment and stabilizes the nitrate-bound metal center.
It is to
be noted that only a few examples of indium-SBU in the
©
2021 American Chemical Society
https://doi.org/10.1021/acs.inorgchem.1c00981
9
238
Inorg. Chem. 2021, 60, 9238−9242

Inorganic Chemistry
pubs.acs.org/IC
Communication
center on the imidazole was exploited for nanomolar TNP
sensing. To the best of our knowledge, no examples of MOFs
having pyramidal NO3− ions in SBUs are reported in the
literature.
cage reveals a hexagonal [In (μ-OH) (NO ) ] sheet capped
1
8
12
3 6
with triangular [In (μ-OH) (NO )] units to form a
9
6
3
cuboctahedron. The capped triangular units are anti to each
−
other, wherein the NO ions are present in the C vertices.
3
3
−
The linker H Imtb was synthesized and characterized
Thus, the NO3 ions’ orientation controls the arrangements of
linear In (μ-OH) within the layers of the MOF.
Further scrutiny of the NO
3
thoroughly by spectroscopic, spectrometric, and elemental
3
2
−
analysis [see SI]. Reactions of H Imtb with In(NO ) ·xH O
3
ion orientation enumerates
3
3 3
2
were carried out under different experimental conditions such
as (a) stoichiometric ratios of ligand to metal (1:1; 1:2; 1:3
etc.), (b) modulating agents, like CH COOH, HNO ,
that it exhibits an atypical pyramidal geometry (Figure 1c).
−
The adjacent NO
ions in hexagonal sheets adopt an anti-
45
3
conformation (like umbrella inversion). Also, within the
layers (a−f), these ions are related to each other by their shape
and the torsional angles between ONNO atoms. Overall, this
3
3
CF COOH, H PO , and HBF , and (c) solvents DMF and
3
3
4
4
DMF/H O mixture. The single crystals of In(Imtb)-MOF
2
suitable for X-ray diffraction (SC-XRD) studies were obtained
in the case of H Imtb, In(NO ) ·xH O (in the ratios 1:2.23,
leads to the formation of a dodecawheel type of arrangement of
−
[(NO
)
4
] ions (Figure 1d).
3
3 3
2
3
1
:3, and 1:4), HBF , and DMF. Analysis of the IR spectrum
Within the indium trimer, the In−O distances of indium
[In1 and In2] and carboxylate ions [In1−O1, 2.145(4) Å;
In1−O3, 2.159(4) Å; In2−O4, 2.141(4) Å; In2−O6, 2.143(5)
Å; In1−O1, 2.145(4) Å; In1−O3, 2.159(4) Å; In1−O5,
4
suggests carboxylate bound to the indium in unidentate (Δ =
−
1
−1
41
2
06 cm ) and bridged (Δ = 150 cm ) modes (Figure S1).
−1
Also, the appearance of a peak at 3645 cm stipulates the
42
2
.186(5) Å; In2−O4, 2.141(4) Å; and In2−O6, 2.143(5) Å]/
presence of the In−OH group. However, the exact structural
details of In(Imtb)-MOF were deduced by SC-XRD (Tables
S1−S3).
The solid-state structure of In(Imtb)-MOF shows a unique
SBU having a composition of [In (μ-OH) (OH ) (NO )-
OH ions [In1−O7, 2.082(4) Å; In2−O7, 2.077(4) Å] or water
molecules [In1−O9, 2.194(7) Å] are well within the reported
4
2
values. However, the In−O bond distance in In-ONO
2
[
In1−O8, 2.081(6) Å] is shorter than the monodentate
9
6
2 6
3
−
46
−
binding of the NO ion to the indium atom [2.143(2) Å].
(
[
(
Imtb) ], in which the NO3 ion with a longer N−O bond
3
6
−
The TGA of activated In(Imtb)-MOF shows thermal
stability up to 480 °C. Also, the VT-PXRD study confirms
the crystallinity of the sample up to 240 °C. The aqueous
stability of the MOF was ascertained for 7 days and
N3−O8:1.477 (6) Å compared to free NO3 (N−O: 1.258
7) Å)] is bridging the three different In (μ-OH) (indium
3
2
40,43,44
trimer) units like the 3.111 type coordination mode.
These indium trimers together with bridged NO3 ions form
−
authenticated through PXRD. The N gas adsorption isotherm
an inorganic hexagonal wave-like pattern [In (μ-
2
1
8
2
gave the calculated BET surface area as 523 m /g (Figure
OH) (NO ) ] (like in tiara), which propagates along the
1
2
3 6
S11−S15a), with an average pore diameter and total pore
volume of 23.71 Å and 0.311 cc/g, respectively. The larger (2
and 3 Å) and the smallest (1.5 Å) pore size reflected in the
NLDFT calculation value can be accounted for by the space
between cuboctahedron and interlayer hexagonal sheets,
respectively (Figure S9e,f).
“
ab” axis to create hexagonal sheets (Figure S9a). Further, the
3−
sheets are linked by (Imtb) to form a 3D network. The
adjacent layers of the 3D network show an offset pattern of
hexagonal indium sheets, which provides a platform for a
cuboctahedral cage [linking In2 of the trimer; Figures 1a,b and
S9b]. A single cuboctahedral nanoporous cage consists of
The gas adsorption studies of CO performed at three
2
[
In (μ-OH) (NO ) (Imtb) ] units. A closer analysis of the
36 24 3 8 24
different temperatures indicate that the adsorption value at 298
K is 1.29 mmol/g (Figure S15b) at 1 bar. Inspired by RT
adsorption, optimization of the cycloaddition reaction of CO2
and epichlorohydrin/styrene oxide using activated MOF as a
catalyst and TBAB as a cocatalyst was carried out at RT/50 °C
1
(
Scheme S2). The H NMR of the reaction mixture showed
complete conversion of the epoxide. Variation of epoxides with
substituents gave excellent conversion as compared to the
blank experiments in all cases (Tables 1 and S4).
Further, solvent-free multicomponent Strecker synthesis of
acetophenone, aniline, and TMSCN in the presence of
In(Imtb)-MOF as a catalyst (0.001 mmol) at RT for 3 h
was studied (Scheme S3; Table S8). A quantitative yield of 2-
phenyl-2-(phenylamino)-propanenitrile was obtained. The
scope of this reaction was evaluated by varying the different
ketones or substituted anilines. In most cases, the yield of the
products was excellent except when electron-withdrawing
groups were present on acetophenone (Table 2). Both
H Imtb and its In(Imtb)-MOF show characteristic lumines-
3
cence in solids at 429 nm (λ 330 nm) and 452 nm (λ 330
ex
ex
nm), respectively. The luminescence intensity of In(Imtb)-
MOF was a maximum under DMSO or DMF solvent, whereas
it is least in nitrobenzene (Figures S59 and S60). Further, the
luminescence of the MOF with different nitrophenols was
evaluated in water, and it shows luminescence quenching with
the highest efficiency (97%) for TNP. Extension of the work to
Figure 1. (a) Cuboctahedron cage, (b) 3D view of In(Imtb)-MOF
connected with (Imtb) , (c) layered nitrate ion arrangements in
MOF, (d) 3D view (starburst).
3−
9
239
https://doi.org/10.1021/acs.inorgchem.1c00981
Inorg. Chem. 2021, 60, 9238−9242

Inorganic Chemistry
pubs.acs.org/IC
Communication
a
formation of pyramidal NO3− ions, except in the IR study of
NO (H O) ions, and the trapping of the ions in any
Table 1. CO Cycloaddition with Different Epoxides
2
3
2
3
48
molecular or framework type of structure is unheard of.
3
−
Also, the (Imtb) and the [In (μ-OH) (NO )] formed in situ
9
6
3
enhanced the thermal and hydrolytic stability of the
cuboctahedral In(Imtb)-MOF. In contrast, the previously
reported cuboctahedral In-MOF with a BTB ligand becomes
49
unstable when exposed to air.
−
Apart from the structural novelty, the NO3 ion plays a vital
role in augmenting the highly dense catalytic surface on the
MOF. There are six catalytic indium centers within the SBU,
extending to form 24 catalytic centers per cuboctahedral unit.
Moreover, each In (μ-OH) consists of a pair of Lewis basic
3
2
(
OH unit/uncoordinated CO units of Imtb) and Lewis
acidic active sites present orthogonally. Together they are
believed to be involved in cooperative cyclization reactions
a
b
1
(
Figure S29). Furthermore, the active sites on indium ions
Epoxide (5 mmol), CO (1 atm.). Conversions based on the H
2
c
NMR spectrum. TOF: TON/total reaction time.
(In1) in given linear In (μ-OH) and [(In (μ-OH) )NO -
3
2
3
2
3
(
In (μ-OH) )] units are in a trans and cis position to each
3 2
a
other. They are well separated by a distance of approximately
.9 and 0.5 nm, respectively. Thus, sterically hindered
Table 2. One-Pot Multicomponent Strecker Synthesis
0
substrates could access the catalytic centers. This was
confirmed by the quantitative conversion of cyclohexene
oxide to the corresponding cyclic carbonate. Most cyclo-
addition reactions barring very few examples, require a higher
,
temperature/pressure of CO2 and excess catalyst loading
(
Tables S6 and S7). However, very low catalyst loading (5
times lower) was required for these conversions. Similarly, in
the Strecker reactions, the sterically hindered substrates, such
as 2,3-/2,5-dimethyl aniline and cyclohexanone, were com-
bined to obtain α-aminonitriles in quantitative yield. The
mechanism of this reaction may be occurring through the
Lewis-acid-catalyzed organic transformation (Figure S56). As
for the Lewis acid sites, there are 24 units of luminescent
3
−
(
Imtb) containing an equal number of free imidazole
nitrogen present in the edges of a cuboctahedron. Such a
large number of acceptor nitrogens and angular donor phenyl
rings in adjacent positions amplify the higher selectivity and
sensitivity toward TNP or other NPs over nonphenolic
50
explosives (Figure S65). A comparison of the In(Imtb)-
MOF with others shows superior sensing and low LOD. The
sensing of TNP by In(Imtb)-MOF started at 0.7 ppb, and the
emission intensity was almost quenched at 32 ppm (efficiency
97%; Table S12). There are only a few MOFs that are known
for nanomolar detection of TNP. Above all, the In(Imtb)-
MOF was recycled for five cycles without losing activity and
crystallinity in each stage of catalysis and TNP sensing.
To summarize, a robust, thermally and hydrolytically stable
In(Imtb)-MOF with a new SBU [In (μ-OH) (NO )] core
9
6
3
−
containing atypical pyramidal NO3 ions is described. Multiple
applications such as solvent-free multicomponent Strecker
a
Ketone, aniline, TMSCN (1.1:1.0:1.1). Based on 1H NMR
b
c
synthesis, preparation of cyclic carbonate using CO as a
spectrum of crude product. TOF = TON/total reaction time.
2
source, and nanomolar sensing of TNP arising out of the
multifunctional group on the pores of MOF are discussed.
Furthermore, the recyclability and reusability of the MOF
qualify for the development of sustainable material for the
future. An extension of the work with other metal ions is under
study.
obtain the LOD gave a value of 2.13 ppb (9.3 nM), suggesting
nanomolar sensing of TNP (Figure S61−S64).
The In(Imtb)-MOF is unique in its structure, properties,
−
and applications, as presented above. The occluded NO3 ion
in the indium trimer in 3.111 coordination provides the first-
36,40
ASSOCIATED CONTENT
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.inorgchem.1c00981.
ever isolation of an anion trapped SBU.
The formations of
■
metal to nitrate bonds are known in the literature. Even the
studies on the hydrolysis of In(NO ) suggest unreacted In-
*
3
2
47
ONO2 ions under a high concentration. However, the
9
240
https://doi.org/10.1021/acs.inorgchem.1c00981
Inorg. Chem. 2021, 60, 9238−9242

Inorganic Chemistry
pubs.acs.org/IC
Communication
Details of experimental methods, structural, crystallo-
(12) Yaghi, O. M.; O’Keeffe, M.; Ockwig, N. W.; Chae, H. K.;
Eddaoudi, M.; Kim, J. Reticular Synthesis and the Design of New
Materials. Nature 2003, 423, 705−714.
graphic, spectral information, and optimization table
PDF)
(
(13) Eddaoudi, M.; Kim, J.; Rosi, N.; Vodak, D.; Wachter, J.;
Accession Codes
O’Keeffe, M.; Yaghi, O. M. Systematic Design of Pore Size and
Functionality in Isoreticular MOFs and Their Application in Methane
Storage. Science 2002, 295, 469−472.
CCDC 2067666 contains the supplementary crystallographic
data for this paper. These data can be obtained free of charge
via www.ccdc.cam.ac.uk/data_request/cif, or by emailing
data_request@ccdc.cam.ac.uk, or by contacting The Cam-
bridge Crystallographic Data Centre, 12 Union Road,
Cambridge CB2 1EZ, UK; fax: +44 1223 336033.
(14) Robson, R. A Net-Based Approach to Coordination Polymers.
J. Chem. Soc. Dalt. Trans. 2000, 3735−3744.
(15) Gable, R. W.; Hoskins, B. F.; Robson, R. A New Type of
Interpenetration Involving Enmeshed Independent Square Grid
Sheets. The Structure of Diaquabis-(4,4′-Bipyridine)Zinc Hexafluor-
osilicate. J. Chem. Soc., Chem. Commun. 1990, 1677−1678.
AUTHOR INFORMATION
Corresponding Author
Ganapathi Anantharaman − Department of Chemistry,
Indian Institute of Technology (IIT) Kanpur, Kanpur
■
(16) Robson, B. F.; Hoskins, R. Design and Construction of a New
Class of Scaffolding-like Materials Comprising Infinite Polymeric
Frameworks of 3D-Linked Molecular Rods. A Reappraisal of the
Zn(CN) and Cd(CN) Structures and the Synthesis and Structure of
2
2
2
08016, India; orcid.org/0000-0001-7740-5581;
Email: garaman@iitk.ac.in
the Diamond-Related Framework. J. Am. Chem. Soc. 1990, 112,
1546−1554.
(17) Ghasempour, H.; Wang, K. Y.; Powell, J. A.; ZareKarizi, F.; Lv,
Author
X. L.; Morsali, A.; Zhou, H. C. Metal−Organic Frameworks Based on
Multicarboxylate Linkers. Coord. Chem. Rev. 2021, 426, 213542.
(18) Tripathi, S.; Anantharaman, G. Architectures Varying from
Discrete Molecular Units to 2-Dimensional Coordination Polymers
and Photoluminescence Behavior of Zinc and Cadmium Comprising
an Anionic Zwitterion of Rigid 4,5-Dicarboxy-1,3-Dimethyl-1H-
Imidazolium Iodide. CrystEngComm 2015, 17, 2754−2768.
Sharad Kumar Sachan − Department of Chemistry, Indian
Institute of Technology (IIT) Kanpur, Kanpur 208016,
India
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.inorgchem.1c00981
(19) Mohapatra, C.; Tripathi, S.; Anantharaman, G.; Chandrasekhar,
Notes
V. A Hexameric Hexagonal Organotin Macrocycle. Supramolecular
Entrapment of an Iodide-Iodide Short Contact. Cryst. Growth Des.
The authors declare no competing financial interest.
2
014, 14, 3182−3185.
ACKNOWLEDGMENTS
Authors thank Science and Engineering Research Board (SERB),
India, and CSIR (SKS) for the financial support (SB/S1/IC-
9/2012) and doctoral fellowship, respectively. They also
thank the Department of Chemistry, IIT Kanpur, for the
infrastructural facility.
■
(20) Kalmutzki, M. J.; Hanikel, N.; Yaghi, O. M. Secondary Building
Units as the Turning Point in the Development of the Reticular
Chemistry of MOFs. Sci. Adv. 2018, 4, No. eaat9180.
(
21) Howarth, A. J.; Liu, Y.; Li, P.; Li, Z.; Wang, T. C.; Hupp, J. T.;
4
Farha, O. K. Chemical, Thermal and Mechanical Stabilities of Metal-
Organic Frameworks. Nat. Rev. Mater. 2016, 1 (15018), 1−15.
(
22) Hong, D. Y.; Hwang, Y. K.; Serre, C.; Férey, G.; Chang, J. S.
Porous Chromium Terephthalate MIL-101 with Coordinatively
Unsaturated Sites: Surface Functionalization, Encapsulation, Sorption
and Catalysis. Adv. Funct. Mater. 2009, 19, 1537−1552.
REFERENCES
■
(
1) Eddaoudi, M.; Sava, D. F.; Eubank, J. F.; Adil, K.; Guillerm, V.
Zeolite-like Metal-Organic Frameworks (ZMOFs): Design, Synthesis,
and Properties. Chem. Soc. Rev. 2015, 44, 228−249.
2) Furukawa, H.; Cordova, K. E.; O’Keeffe, M.; Yaghi, O. M. The
Chemistry and Applications of Metal-Organic Frameworks. Science
013, 341 (1−16), 1230444.
3) Wang, C.; Liu, D.; Lin, W. Metal-Organic Frameworks as a
Tunable Platform for Designing Functional Molecular Materials. J.
Am. Chem. Soc. 2013, 135, 13222−13234.
4) Lee, J.; Farha, O. K.; Roberts, J.; Scheidt, K. A.; Nguyen, S. T.;
(
23) Pal, T. K.; De, D.; Bharadwaj, P. K. Metal−Organic
Frameworks for the Chemical Fixation of CO into Cyclic
2
(
Carbonates. Coord. Chem. Rev. 2020, 408, 213173.
(24) Cui, Y.; Li, B.; He, H.; Zhou, W.; Chen, B.; Qian, G. Metal-
2
(
Organic Frameworks as Platforms for Functional Materials. Acc.
Chem. Res. 2016, 49, 483−493.
(25) Li, B.; Wen, H. M.; Cui, Y.; Zhou, W.; Qian, G.; Chen, B.
Emerging Multifunctional Metal−Organic Framework Materials. Adv.
(
Mater. 2016, 28, 8819−8860.
Hupp, J. T. Metal-Organic Framework Materials as Catalysts. Chem.
Soc. Rev. 2009, 38, 1450−1459.
5) Allendorf, M. D.; Bauer, C. A.; Bhakta, R. K.; Houk, R. J. T.
(26) Elango, K.; Avinash, I.; Sachan, S. K.; Anantharaman, G.
Hydrolysis of NHC Stabilized Zinc Diaryloxide [(NHC)Zn(OAr)2]:
Impact of Stoichiometric Quantity of Water and Base. J. Organomet.
Chem. 2019, 893, 78−84.
(
Luminescent Metal-Organic Frameworks. Chem. Soc. Rev. 2009, 38,
1
(
−
330−1352.
(27) Anantharaman, G.; Elango, K. Synthesis and Characterization
6) Natarajan, S.; Mahata, P. Metal−Organic Framework Structures
of NHC-Stabilized Zinc Aryloxide and Zinc Hydroxyaryloxide.
How Closely Are They Related to Classical Inorganic Structures?
Organometallics 2007, 26, 1089−1092.
Chem. Soc. Rev. 2009, 38, 2304−2318.
7) Férey, G. Hybrid Porous Solids: Past, Present, Future. Chem. Soc.
Rev. 2008, 37, 191−214.
8) Maji, T. K.; Kitagawa, S. Chemistry of Porous Coordination
Polymers. Pure Appl. Chem. 2007, 79, 2155−2177.
9) Cheetham, A. K.; Rao, C. N. R.; Feller, R. K. Structural Diversity
and Chemical Trends in Hybrid Inorganic-Organic Framework
Materials. Chem. Commun. 2006, 46, 4780−4795.
10) Kitagawa, S.; Kitaura, R.; Noro, S. I. Functional Porous
(28) Bradley, D. C.; Mehrotra, R. C.; Rothwell, I. P.; Singh, A.
(
Alkoxo and Aryloxo Derivatives of Metals; Elsevier, 2001; pp 445−669,.
(29) Cochran, E. A.; Woods, K. N.; Johnson, D. W.; Page, C. J.;
(
Boettcher, S. W. Unique Chemistries of Metal-Nitrate Precursors to
Form Metal-Oxide Thin Films from Solution: Materials for Electronic
and Energy Applications. J. Mater. Chem. A 2019, 7, 24124−24149.
(30) Winarta, J.; Shan, B.; McIntyre, S. M.; Ye, L.; Wang, C.; Liu, J.;
Mu, B. A Decade of UiO-66 Research: A Historic Review of Dynamic
Structure, Synthesis Mechanisms, and Characterization Techniques of
an Archetypal Metal-Organic Framework. Cryst. Growth Des. 2020,
20, 1347−1362.
(
(
Coordination Polymers. Angew. Chem., Int. Ed. 2004, 43, 2334−2375.
11) Kitagawa, S.; Kitaura, R.; Noro, S. Funktionale Porose
Koordinationspolymere. Angew. Chem. 2004, 116, 2388−2430.
(
̈
9
241
https://doi.org/10.1021/acs.inorgchem.1c00981
Inorg. Chem. 2021, 60, 9238−9242

Inorganic Chemistry
pubs.acs.org/IC
Communication
(
31) Schaate, A.; Roy, P.; Godt, A.; Lippke, J.; Waltz, F.; Wiebcke,
(49) Goebbert, D. J.; Garand, E.; Wende, T.; Bergmann, R.; Meijer,
M.; Behrens, P. Modulated Synthesis of Zr-Based Metal-Organic
Frameworks: From Nano to Single Crystals. Chem. - Eur. J. 2011, 17,
G.; Asmis, K. R.; Neumark, D. M. Infrared Spectroscopy of the
−
Microhydrated Nitrate Ions NO3 (H O)1−6. J. Phys. Chem. A 2009,
2
6
(
643−6651.
113, 7584−7592.
32) Diring, S.; Furukawa, S.; Takashima, Y.; Tsuruoka, T.;
(50) Sharma, A.; Kim, D.; Park, J. H.; Rakshit, S.; Seong, J.; Jeong,
G. H.; Kwon, O. H.; Lah, M. S. Mechanistic Insight into the Sensing
of Nitroaromatic Compounds by Metal-Organic Frameworks.
Commun. Chem. 2019, 2, 1−8.
Kitagawa, S. Controlled Multiscale Synthesis of Porous Coordination
Polymer in Nano/Micro Regimes. Chem. Mater. 2010, 22, 4531−
4
538.
(
33) Tsuruoka, T.; Furukawa, S.; Takashima, Y.; Yoshida, K.; Isoda,
S.; Kitagawa, S. Nanoporous Nanorods Fabricated by Coordination
Modulation and Oriented Attachment Growth. Angew. Chem., Int. Ed.
2
009, 48, 4739−4743; Nanoporous Nanorods Fabricated by
Coordination Modulation and Oriented Attachment Growth.
Angew. Chem. 2009, 121, 4833−4837.
(
34) Aguirre-Díaz, L. M.; Reinares-Fisac, D.; Iglesias, M.; Gutiérrez-
́
Puebla, E.; Gándara, F.; Snejko, N.; Monge, M. A. Group 13th Metal-
Organic Frameworks and Their Role in Heterogeneous Catalysis.
Coord. Chem. Rev. 2017, 335, 1−27.
(
35) Schilling, L. H.; Reinsch, H. S.; Stock, N. In The Chemistry of
Metal−Organic Frameworks; Kaskel, S., Ed.; Wiley: Hoboken, NJ,
016.
36) Zheng, S. T.; Bu, J. J.; Wu, T.; Chou, C.; Feng, P.; Bu, X.
2
(
Porous Indium-Organic Frameworks and Systematization of Struc-
tural Building Blocks. Angew. Chem., Int. Ed. 2011, 50, 8858−8862;
Porous Indium-Organic Frameworks and Systematization of Struc-
tural Building Blocks. Angew. Chem. 2011, 123, 9020−9024.
(
37) Fridman, N.; Speiser, S.; Kaftory, M. Structures and
Chromogenic Properties of Bisimidazole Derivatives. Cryst. Growth
Des. 2006, 6, 1653−1662.
(38) Nakashima, K. Lophine Derivatives as Versatile Analytical
Tools. Biomed. Chromatogr. 2003, 17, 83−95.
39) MacDonald, A.; Chain, K. W.; Nieman, T. A. Lophine
Chemiluminescence for Metal Ion Determinations. Anal. Chem. 1979,
1, 2077−2082.
40) Goura, J.; Chandrasekhar, V. Molecular Metal Phosphonates.
Chem. Rev. 2015, 115, 6854−6965.
41) Nakamoto, K. Applications in Inorganic Chemistry. In Infrared
(
5
(
(
and Raman Spectra of Inorganic and Coordination Compounds Part B:
Theory and Applications in Inorganic Chemistry; Wiley: Hoboken, NJ,
2
08AD.
42) Anokhina, E. V.; Vougo-Zanda, M.; Wang, X.; Jacobson, A. J. In
OH)BDC 0.75BDCH2 (BDC) Benzenedicarboxylate), a Hybrid
Inorganic - Organic Vernier Structure. J. Am. Chem. Soc. 2005, 127,
5000−15001.
43) Tripathi, S.; Srirambalaji, R.; Patra, S.; Anantharaman, G. Anion
(
(
1
(
Triggered and Solvent Assisted Structural Diversity and Reversible
Single-Crystal-to-Single-Crystal (SCSC) Transfor mation between 1D
and 2D Coordination Polymers. CrystEngComm 2015, 17, 8876−
8
(
887.
44) Tripathi, S.; Srirambalaji, R.; Singh, N.; Anantharaman, G.
Chiral and Achiral Helical Coordination Polymers of Zinc and
Cadmium from Achiral 2,6-Bis(Imidazol-1-Yl)Pyridine: Solvent Effect
and Spontaneous Resolution. J. Chem. Sci. 2014, 126, 1423−1431.
(45) Huheey, J. E.; Keiter, E. A.; Keiter, R. L.; Medhi, O. K.
Inorganic Chemistry: Principles of Structure and Reactivity; Harper
Collins College Publishers: New York, 2006.
(46) Chen, S.; Fan, R.; Wang, X.; Yang, Y. A Novel Blue-Emitting
Indium (III) Complex: Synthesis, Crystal Structure, and Effect of
Solvents and Temperature on the Luminescent Properties. Inorg.
Chem. Commun. 2014, 44, 101−106.
(47) Rudolph, W. W.; Fischer, D.; Tomney, M. R.; Pye, C. C.
Indium(III) Hydration in Aqueous Solutions of Perchlorate, Nitrate
and Sulfate. Raman and Infrared Spectroscopic Studies and Ab-Initio
Molecular Orbital Calculations of Indium(III)−Water Clusters. Phys.
Chem. Chem. Phys. 2004, 6, 5145−5155.
(48) Yu, P.; Li, Q.; Hu, Y.; Liu, N.; Zhang, L.; Su, K.; Qian, J.;
Huang, S.; Hong, M. Cuboctahedron-Based Indium−Organic Frame-
works for Gas Sorption and Selective Cation Exchange. Chem.
Commun. 2016, 52, 7978−7981.
9
242
https://doi.org/10.1021/acs.inorgchem.1c00981
Inorg. Chem. 2021, 60, 9238−9242