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N-Functionality Actuated Largely Improved CO 2 Adsorption and Nanomolar

Turn-on Detection of Organo-Toxins with Guest-Induced Fluorescence
Modulation in Isostructural Diamondoid Fr...

Article in Journal of Materials Chemistry C · June 2021

DOI: 10.1039/D1TC01123E

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N-Functionality actuated improved CO2

adsorption and turn-on detection of
Cite this: J. Mater. Chem. C, 2021,
9, 7142 organo-toxins with guest-induced fluorescence
modulation in isostructural diamondoid MOFs†
ab c
Manpreet Singh, Athulya S. Palakkal, Renjith S. Pillai *c and
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ab
Subhadip Neogi *

Functional-group-assisted pore environment modulation in metal–organic frameworks (MOFs) can

support the substantial development of their applications, and structure–property synergy can be best
described via comparisons between isoskeletal MOFs that differ in functionality. Herein, we elaborate
the effects of functional disparity on selective carbon dioxide (CO2) adsorption and the luminescence
detection of lethal pollutants using a pair of structurally similar and 4-fold interpenetrated dia-networks,
CSMCRI-7 and CSMCRI-8 (CSMCRI = Central Salt & Marine Chemicals Research Institute), that vary by a
spare nitrogen atom in the constituent bifunctional struts. Pore-wall decoration with accessible triazole
ring N-atoms nearly doubles the CO2 uptake capacity in desolvated CSMCRI-8 (8a) with a 10.9 kJ mol1
rise in adsorption enthalpy compared to 7a. Interestingly, CO2 selectivity over N2 (322.2) displays a two-
fold enhancement, validating the strong effects of channel functionalization; this is further supported
via microscopic adsorption mechanism studies based on grand canonical Monte Carlo simulation.
Benefiting from a strong emission signature and nitrogen-rich pore surface, 8a represents the first-ever
turn-on luminescent MOF (LMOF) for highly specific, recyclable and fast responsive detection of toxic
3-(diethylamino)phenol (DEP) and the lethal pesticide isoproturon (IPT), with nanomolar limit of detec-
tion (LOD) values (DEP: 79.8 nM; IPT: 226 nM). Importantly, guest-responsive fluorescence modulation is
evidenced through the remarkable turn-off sensing of the pesticide dichloran with admirable selectivity,
Received 10th March 2021, a quick response time, and a very low LOD (124 nM), with sharp colorimetric changes under UV light.
Accepted 7th May 2021 The accessibility of the nitrogen sites plays a crucial role in the sensing performance, which is supported
DOI: 10.1039/d1tc01123e by periodic-density functional theory (DFT) calculations, with the unique shuffling of the molecular
orbital energy levels of the diamondoid MOFs in the presence of each organo-aromatic, further demon-
[Link]/materials-c strating superior framework-analyte non-covalent interactions in the pore-engineered structure.

Introduction interest in academia and industry owing to their enormous

structural diversity, the ability to purposefully implant active
Metal–organic frameworks (MOFs), as a burgeoning class of sites, and the prospect of structure–property correlations.1,2 In
crystalline porous materials, have gained considerable research particular, applications that aim to address environmental
issues like separation, catalysis, gas storage, and sensing, have
become hot areas of study, with the possibility of task-specific
a
Inorganic Materials & Catalysis Division, CSIR-Central Salt and Marine Chemicals pore-environment modulation.3–8 For example, MOFs with
Research Institute (CSMCRI), Bhavnagar, Gujarat 364002, India.
designable pores have become an attractive platform for selec-
E-mail: sneogi@[Link]
b
Academy of Scientific and Innovative Research (AcSIR), Ghaziabad-201002, India
tively adsorbing CO2, and they show promise to overcome the
c
Department of Chemistry, SRM Institute of Science and Technology, challenges related to amine-based sorbents.9,10 With this in
Kattankulathur, Tamil Nadu 603203, India. E-mail: renjiths@[Link] mind, strategies like pore-surface decoration with strongly
† Electronic supplementary information (ESI) available: Materials, methods and polarizing basic groups and interpenetration-induced pore-
physical measurements, additional structural figures, PXRD patterns, TGA curves,
size optimization are the best known for enhancing molecule-
Fourier-transform infrared spectra, adsorption isotherms, UV-vis and fluores-
cence spectra, ICP data, Computational Modelling and tables and tables (PDF).
specific interactions.11–14 Further, luminescent MOFs (LMOFs)
CCDC 2064805 and 2064806. For ESI and crystallographic data in CIF or other with abundant functional sites have emerged as smart scaffolds
electronic format see DOI: 10.1039/d1tc01123e for specifically detecting hazardous chemicals from industry,

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especially toxic organo-aromatics.15–17 In this area, the amino

phenolic compound 3-(diethylamino)phenol (DEP) is highly
poisonous and widely produced in the pharmaceutical, dye,
and polymer trades.18–20 The broad utilization of pesticides in
agriculture and animal farming, coupled with their slow degra-
dation rates, makes them acutely harmful to human beings,
with the risk of ecological contamination.21,22 In particular, the
carcinogenic pesticide isoproturon (IPT) and the organochlor-
ine 2,6-dichloro-4-nitroaniline (dichloran) belong to toxicity
class III, and are most harmful to humans.23,24 Given that the
detection of these organic pollutants has long been accomplished
via the use of costly and cumbersome instrumentation-based
methods, the major benefits of LMOFs include their easy port-
ability, simple operational procedures, high selectivities, and quick
response times.25,26 Here it may be noted that the majority of
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LMOFs operate via a fluorescent quenching mechanism that

allows turn-on detection;27 this is a sensitive and rather desirable
method, as the naked eye can quickly recognize a color change
from a relatively dark background.28,29
Fig. 1 (a) A single diamondoid cage in CSMCRI-8 and (b) the four-fold
Considering the above issues, the fabrication of a versatile interpenetration. (c) A perspective view of the pores along the b axis and
MOF that can selectively capture CO2 and precisely detect (d) a tilted view of the structure along the b axis, displaying no voids along
multiple classes of lethal pollutants via unique fluorescence the a or c axis.
fingerprints, will not only save time and energy but also provide
a step forward in terms of environmental remediation appli-
superiority in fluoro-sensing in the case of the N-functionalized
cations.30–33 To this end, the utilization of bifunctional ligands,
MOF is comprehensively validated based on Perdew–Burke–
incorporating both azolate-heterocycle and carboxylate donors,
Ernzerhof (PBE) functional based density functional theory
has contributed to the devising of high-performing MOFs for
(DFT) calculation studies.47
multifaceted sustainable applications with minimum sacrifices
in terms of pore surface.24,34–37 An interesting modification
approach for amplifying the performance characteristics is to Results and discussion
confer heterogeneity on the pore environment via incorporating
bifunctional linkers into the MOF skeleton with diverse functional Structure, framework stability, and porosity properties of
groups (tags) while preserving the structural connectivity.38–41 diamondoid MOFs
However, convincing conclusions can only be drawn from direct Both the bifunctional ligands, 4-imidazol-1-yl-benzoic acid (HL1)
comparisons between MOFs with identical structures and and 4-[1,2,4]triazol-1-yl-benzoic acid (HL2), share similar chemical
topologies, differing only in the nature of functionalization. structures (Scheme S1, ESI†), with the difference being that the
Unfortunately, such an approach is still rare in the MOF latter is equipped with an extra nitrogen site in the triazole moiety.
literature because of the unfavorable binding of additional This particular feature leads the second N atom of the triazole ring
functionality with the metal ions of concern.42–44 With a view to remain uncoordinated in the resulting Cd(II)-framework
to imparting additional functionality and manipulating the CSMCRI-8 (CSMCRI = Central Salt & Marine Chemicals Research
electronic properties of a MOF towards selective CO2 adsorption Institute), while the structurally similar CSMCRI-7, encompassing
and the luminescence detection of lethal pollutants, we used a HL1 ligands, represents the unfunctionalized analogue (Table S4,
pair of isostructural and 4-fold interpenetrated diamondoid ESI†). Owing to the presence of a sharp kink in the bifunctional
Cd(II)-frameworks that were previously reported by Aizaz struts, both structures exhibit diamondoid networks (Fig. 1a),
et al.45 and Li et al.46 In spite of their structural similarity, having sqc6-net with the Schlafli symbol {6^6} (Fig. S1, ESI†),48
pore-wall decoration with the free N-atoms of triazole rings in and the construction is different from other non-catenated
one of the MOFs leads to a tremendous upsurge in the CO2 frameworks.36,49 As depicted in Fig. 1a, a single diamond cage
uptake capacity along with a large rise in the adsorption is assembled from 12 L2 struts and 10 single Cd(II) nodes, with
enthalpy compared to the unfunctionalized analogue. Impor- Cd  Cd separations of 12.33 Å and 12.49 Å (the distances refer to
tantly, the CO2 selectivity over other gases exhibits a two-fold the atom to atom connections throughout). Such large open space
increase, while the CO2/N2 selectivity has an exceptional value of allows 4-fold interpenetration (Fig. 1b) in the overall structure,
322.2. Sensing studies show the first-ever example of the turn-on leaving no voids along the a or c axis (Fig. 1d). Even after
detection of toxic 3-(diethylamino)phenol (DEP) and the lethal interpenetration, the framework possesses one-dimensional, rec-
pesticide isoproturon (IPT) using both luminescent MOFs (LMOFs), tangular channels with dimensions of 13.93  12.30 Å2 extending
with guest-responsive emission modulation shown through the along the crystallographic b axis (Fig. 1c). The solvent-accessible void
turn-off detection of the pesticide dichloran. The distinctive volume calculated via PLATON50 is 41.9%. The extra-framework

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Fig. 2 The PXRD curves of the as-synthesised frameworks (a) CSMCRI-7 and (b) CSMCRI-8 in different organic solvents.
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DMF molecules are positioned nearly at the middle of these voids Gas adsorption studies
(Fig. S1, ESI†) and are involved in hydrogen bonding interactions The CO2 adsorption capacities of the activated MOFs were
with the walls of the host framework. measured up to 1 bar pressure at diverse temperatures. Reversible
Powder X-ray diffraction (PXRD) patterns of the bulk sam- type-I isotherms (Fig. 3) with steep CO2 uptake in the low-pressure
ples exhibit the complete coherence of the peak positions with region (0.1 bar) corroborate the existence of microporous
those in the simulated patterns (Fig. S2, ESI†) derived from structures. The CO2 uptake for 7a at 273 K is 28.29 cm3 g1
individual single-crystal X-ray data. Thermogravimetric analysis (1.26 mmol g1). Surprisingly, the amount of CO2 adsorption
(TGA) showed two-step weight loss (Fig. S4, ESI†) under a N2 under identical measurement conditions almost doubles in 8a
atmosphere for both CSMCRI-7 (16.62%) and CSMCRI-8 (53.65 cm3 g1/2.40 mmol g1). Given the similar structures
(16.24%), corresponding to the release of lattice guest solvents, and pore apertures, such a high rise in CO2 adsorption is rather
followed by a distinct plateau, and the stability remains unaffected unprecedented. Further, CO2 adsorption isotherms (Fig. S6,
even above 300 1C. For both frameworks, the PXRD patterns at ESI†) at 298 K also follow a similar trend, showing an uptake of
higher temperatures (150 and 200 1C) remain unchanged (Fig. S2, 16.11 cm3 g1 (0.72 mmol g1) for 7a and an uptake of
ESI†) with no shifts in the Bragg reflections, as opposed to the 29.23 cm3 g1 (1.30 mmol g1) for 8a.55,56 It is imperative to
majority of interpenetrated (flexible) structures.51,52 In the inter- note that despite a low BET surface area, the CO2 adsorption
penetrated structure, adjacent diamondoid nets are held together capacity of 8a is superior to other reported MOFs with much
by ample p  p stacking interactions between the benzene and larger surface areas, including SNU-15, (Table S8, entry 3, ESI†),
triazole rings of the struts, which confer rigidity on the overall LiB(4-MIm)4, CuB(4-MIm)4 (Table S8, entry 4, ESI†), SNU-6
framework.53 We subsequently checked the effects of common (Table S8, entry 26, ESI†), and MAC-4 (Table S8, entry 34, ESI†).
organic solvents (dichloromethane, acetonitrile, acetone, chloro- Such marked differences in CO2 uptake values can be related to
form, and methanol) on the framework stabilities via soaking the integration of additional heteroatoms in L2, leading to pore
individual MOF crystals in these solvents for one week. wall decoration in 8a with accessible N-functionalities. These
The resultant PXRD curves showed no alternations in peaks Lewis basic sites strongly interact with CO2 molecules. A close
(Fig. 2a and b). However, the slight differences in peak intensities comparison of the pore characters of the individual diamond
for CSMCRI-7 in acetone and acetonitrile solvents imply partial cage structures revealed that the free N-atoms of L2 are directed
changes in crystallinity. The high-boiling-point DMF guests in the inward for CSMCRI-8 (Fig. 1), while such functionalization is
as-synthesized crystals were exchanged with dichloromethane, absent in CSMCRI-7 (Fig. S1, ESI†). Further interpenetration
and guest-free frameworks (7a and 8a) were obtained upon in the framework principally augments the uncoordinated
heating the solvent-exchanged crystals at 120 1C for four hours, N-atoms four-fold per cavity, which in turn favours better CO2
followed by overnight degassing under vacuum. For every adsorption in 8a.36
desolvated framework, the {CQO (carbonyl) band of lattice
DMF molecules was absent in the FT-IR spectrum (Fig. S3,
ESI†). In addition, no weight loss was witnessed in TGA Computational validation
analysis up to 300 1C (Fig. S4, ESI†), and the PXRD patterns To further support the above verdict, computational studies were
revealed unaltered profiles (Fig. S2, ESI†). These observations performed via grand canonical Monte Carlo (GCMC) simulations.
corroborate the complete maintenance of the structural The density plots revealed that the occupation position of CO2 is
integrities in the activated forms. The Brunauer–Emmett–Teller maximum in the centres of the pores for each of the diamondoid
(BET) surface areas of 7a and 8a were measured from N2 frameworks (Fig. 3e, f and Fig. S8, ESI†). Moreover, analysis of the
adsorption isotherms (Fig. S5, ESI†) at 77 K up to a relative microscopic CO2 adsorption mechanisms for both isostructural
pressure (p/p0) of 1.0, revealing values of 19 and 23 m2 g1, MOFs was conducted via GCMC simulation, clearly revealing
respectively.54 that N-functionality actuated the superior adsorption capacity of

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Fig. 3 The adsorption isotherms for CO2, N2, and CH4 for (a) 7a and (b) 8a at 273 K. (c) The heat of adsorption curves for the isostructural MOFs. (d) CO2/
N2 and CO2/CH4 IAST selectivity plots for 7a and 8a at 273 K. The diverse framework-CO2 interactions in (e) 7a and (f) 8a, obtained from GCMC
simulation, validating the superior performance of the N-functionalized framework.

8a over unfunctionalized 7a. For 8a, CO2 molecules interact oxygen and uncoordinated nitrogen atoms of the triazole ring
strongly with accessible N atoms in L2, having mean characteristic in 8a interact strongly with the CO2 molecules (Fig. S9, ESI†),
CCO2–NL2 and OCO2–HL2 distances of 3.0 and 2.8 Å, respectively, leading to superior host–guest interactions than in the case of 7a.
favoring the uptake of more CO2 molecules inside its 1D channels
with functionalized pores (Fig. 3f). However, these strong interac- CO2 heat of adsorption and selectivity studies
tions are absent in 7a, and the comparatively less-effective aro- For a better understanding of these observations and to validate
matic hydrogen and carbon atoms of L1 are involved in the computational outcomes, isosteric heats of CO2 adsorption
interactions with CO2 (Fig. 3e). The density plot (Fig. S8, ESI†) (Qst) were considered for 7a and 8a using the Clausius–
further depicts that adsorbed CO2 molecules are oriented towards Clapeyron equation based on adsorption isotherms at two different
the centres of the porous channels in both of the MOFs, where a temperatures.57 As shown in Fig. 3c, the adsorption enthalpy for
noticeable tilt of the adsorbate towards the N-functionalized 8a (34.92 kJ mol1) is B11 kJ mol1 higher than that of 7a
pore-wall in the case of 8a corroborates the greater association (24.02 kJ mol1) at zero loading. Such an increased Qst value
between the CO2 molecules and the framework. The radial evidently highlights the significant role of N-functionalization
distribution functions (RDFs) indicate that both carboxylate in providing additional interaction sites for polar adsorbate

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Fig. 4 (a) Fluorescence quenching/enhancement efficiencies of 7a and 8a (1 mg/2 mL DMF) for different aminophenols. (b) Luminescence spectra of 8a
upon the gradual addition of 1 mM DEP solution (the inset shows the colorimetric changes of the MOF dispersion before and after the addition of DEP
under 365 nm UV light). (c) A S–V plot for 8a upon the incremental addition of DEP (the inset displays the linear region of the S–V plot). (d) S–V plots for all
studied aminophenols (1 mM) upon titration with well-dispersed suspensions of 8a and (e) interference plots showing the changes in PL intensities upon
the addition of different aminophenols, followed by DEP.

molecules. Thereafter, the Qst values decrease slightly due to the CH4 (Fig. 3d) were evaluated for 7a and 8a from single-component
filling of the sites with maximum affinity, and then they remain isotherms at 273 K using ideal adsorbed solution theory (IAST).58
steady, even at higher coverages (Fig. 3c). The Qst value for 8a The selectivity over N2 (CO2/N2 = 15 : 85 mol ratio) for 7a is calculated
is superior to many of known MOFs, including UiO-66-1,4- to be as high as 157.6, while the CO2/CH4 (15 : 85 mol ratio)
naphthyl (Table S8, entry 6, ESI†), UiO-66(Hf)-(F)4 (Table S8, selectivity is found to be 6.1. To our surprise, pore engineering with
entry 10, ESI†), [Cu2(BDPT4)(H2O)2] (Table S8, entry 13, ESI†), free N-atoms leads to a two-fold improvement in CO2/N2 selectivity
[Cu2PDAI(H2O)] (Table S8, entry 15, ESI†), TTF-4 (Table S8, entry in 8a (322.2), whereas the CO2/CH4 (15 : 85 mol ratio) selectivity
25, ESI†), UMCM-1 (Table S8, entry 29, ESI†), MOF-5 (Table S8, (10.0) also experiences a sharp increase. Given that a handful of
entry 30, ESI†), NU-1000 (Table S8, entry 33, ESI†), and MAC-4-OH MOFs have shown such remarkable CO2/N2 selectivity (4300), this
(Table S8, entry 34, ESI†). Subsequently, CO2 selectivity over N2 and result truly justifies the concept of N-functionalization-actuated

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superior adsorption with largely enhanced CO2 selectivity in an enhancement effect upon the incremental addition of 10 mM
isostructural diamondoid framework. DEP solution to a dispersion of activated CSMCRI-8 (Fig. S13,
ESI†). Using the equation 3s/K (s = the standard deviation
The turn-on and nanomolar fluoro-sensing of aminophenol of the initial intensity of 8a over five successive blank measure-
These isostructural MOFs, encompassing electronically passive ments without analyte at 2 min intervals and K = the slope of
Cd(II) ions and p-conjugated bifunctional ligands, display an the linear curve in Fig. S14, ESI†),64 the LOD value for DEP
intense photo-luminescence (PL) signature at 338 nm (for 7a) or turned out to be 79.8 nM (39 ppb) (Table S5, ESI†). Such an
329 nm (for 8a) upon excitation at 272 nm (Fig. S10, ESI†). Both extremely low LOD truly corroborates the ultra-sensitivity of 8a,
MOFs exhibit ligand-centred emission with a large enhance- and this value ranks as one of the best among LMOFs that are
ment in the optical responses (Fig. S10, ESI†).59 This originates used for the turn-on detection of other lethal pollutants.
from the collective contribution of ligand-to-ligand charge Surprisingly, 4-AP showed a clear decline in the PL intensity,
transfer transitions (LLCTs) (n–p* and p–p* transitions),60,61 indicating a turn-off response, with quenching efficacies of
extensive p–p stacking interactions between adjacent aromatic 26.3% and 28.4% for 7a and 8a, respectively (Fig. S11 and S12,
struts in the interpenetrated structure (vide supra), and intra- ESI†), indicating the possibility of analyte-responsive emission
ligand charge-transfer transitions involving aromatic struts.62 modification by means of suitable interactions.
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The maximum fluorescence intensities shown by these LMOFs

in DMF confirmed that this solvent is best-suited for all fluoro- The selectivity, recyclability, and fast response toward DEP
sensing studies (Fig. S10, ESI†). Importantly, upon the removal sensing
of dispersed LMOF, the filtrate does not show fluorescence in With this knowledge of nanomolar sensing, we verified the
either case, indicating that the emission originates from MOF selective detection of DEP by 8a in the presence of interfering
particles only and also discarding any chance of leaching. amino-phenols through competitive analysis testing (CAT).26,65
Based on this notable luminescence coupled with our quest As divulged in Fig. S15 (ESI†), the initial emission intensity of
to study the N-functionality-mediated variations in sensing 8a is trivially affected by the addition of 60 mL of interfering
performance,36 we investigated the sensing abilities of 7a and amino-phenols. In contrast, the immediate incorporation of
8a towards diverse aminophenolic compounds (Scheme S2, DEP improved the optical signal drastically (Fig. 4e). These
ESI†) (1 mM) (Fig. S11 and S12, ESI†) via titration (20–120 mL) results clearly portray the outstanding efficacy of the framework for
with well-dispersed MOF solutions (1 mg in 2 mL of DMF) at solely identifying DEP, wherein interference from other amino-
room temperature. As shown in Fig. 4a, the fluorescence phenols can be nullified. Anti-interference tests over successive
intensity of 7a increased radically (13.4-fold) upon the incremental cycles revalidated the highly discriminative luminescence
addition of 3-(diethylamino)phenol (DEP) solution. Impressively, recognition of DEP. Consequently, we checked the multicyclic
pore-wall-functionalized 8a revealed an outstanding 17.7-fold usability of the framework. Dispersed particles of 8a were
enhancement in turn-on emission. In fact, such a huge enhance- recovered via centrifugation after experiment, washed thoroughly
ment of the optical signal is unprecedented, which results in the with fresh DCM, air-dried, and reused. Gratifyingly, recycled 8a
shoulder peak at 425 nm completely disappearing. Also, the entirely regained its original PL intensity, and the further addition
addition of 3-(dimethylamino)phenol (DMP) results in improve- of DEP triggered the expected fluorescence turn-on responses for
ments in the optical responses of 7a and 8a by 12.6- and 15.2-fold, up to five sensing-recovery cycles (Fig. S16, ESI†). It is worth
respectively. To the best of our knowledge, this is the first report of mentioning that the framework integrity of recycled 8a is preserved
an N-alkylated amino-phenol sensory MOF with such improved during sensing-recovery cycles, as established by its unchanged
optical signals. Such noticeable disparities in the emission PXRD pattern (Fig. S17, ESI†). To examine the practical usability of
turn-on intensities between the two structurally similar MOFs the MOF sensor, we tested the changes in the emission intensity
can be attributed to superior N-functionality-actuated inter- percentages of 8a with respect to the response time via fast-
actions between the analyte and 8a (vide infra). Considering responsive analyte testing (FRAT).26 A drastic 9.5-fold emission
various other amino-phenols (3-aminophenol (3-AP) and 2-amino- enhancement was perceived in just 20 s upon the addition of
phenol (2-AP)), the enhancement efficiencies were found to be in only 40 mL of DEP to a MOF dispersion under continuous
the following order: DEP 4 DMP c 3-AP 4 2-AP. Given that the stirring (Fig. S18, ESI†). Under these invariable experimental
degree of PL intensity change is highest for 8a, the enhancement conditions, emission spectra were recorded for up to 120 s
constant (KEC) is measured for this LMOF as per the equation (at intervals of 20 s) that displayed negligible variations in PL
(F/F0) = 1 + KEC[Q] (F and F0 are the fluorescence intensities after intensity, and this conceivably demonstrates the fast response
and before the addition of DEP, respectively; and [Q] is the of 8a even at a very low concentration of DEP.
molar concentration of analyte).63 KEC was calculated from the
linear region of a plot of F/F0  1 vs. concentration (Fig. 4c) in The ultrasensitive detection of dichloran and isoproturon
the lower concentration range (0.0–0.03 mM). The value of pesticides
3.74  105 M1 ranks as one of the best among all turn-on Building on the ultra-sensitive detection of amino-phenol, we
responsive LMOFs, and additionally supports the idea of strong studied the emission behaviour of these MOFs towards harmful
interactions between DEP and 8a. Furthermore, quantification pesticides (Scheme S3, ESI†) like isoproturon (IPT), hexaconazole
of the limit of detection (LOD) was obtained via monitoring the (HCL), diuron (DUN), 2,6-dichloro-4-nitroaniline (dichloran),

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Fig. 5 Luminescence spectra of 8a upon the gradual addition of 5 mM solutions of (a) IPT and (b) dichloran (DCNA) (the insets show the colorimetric changes of the
MOF dispersions before and after the addition of analytes under 365 nm UV light). (c) Fluorescence quenching/enhancement efficiencies of 7a and 8a (1 mg/2 mL of
DMF) for different pesticides. (d) Fast-responsive analyte testing involving DCNA. (e) S–V plots for all studied pesticides (5 mM) upon titration with well-dispersed
suspensions of 8a. (f) Interference plots showing changes in the PL intensities upon the addition of different pesticides (5 mM, 120 mL), followed by DCNA.

2,4-dichlorophenol (DCP), and 2,4,40 -trichloro-2 0 -hydroxydiphenyl emission enhancement for 7a and 8a, respectively (Fig. 5c).
ether (TCHDE), following the above protocol. Surprisingly, Noticeably, both these frameworks demonstrate the first-ever
dichloran (5 mM in DMF) resulted in remarkable fluorescence detection method for the pesticide IPT, and this work represents
quenching levels of 95.8% and 99.5% for 7a and 8a, respectively. a rare instance of luminescence modulation through turn-off/on
Similar to amino-phenol detection, these results again endorse responses toward two pesticides. Detailed experimental studies
the differences in sensing attributes between 7a and 8a as a were carried out with 8a, since this MOF showed superior
consequence of functionalization. Apart from titration experi- chemo-sensing abilities toward both pesticides.15,21,66 The
ments, a sharp reduction in the PL intensity was also visually quantification of PL quenching in response to dichloran was
monitored under UV-light (365 nm), wherein the bright glow of obtained from the Stern–Volmer (S–V) equation:67 (F0/F) = 1 +
8a in the cuvette immediately faded upon dichloran addition KSV[Q]. The non-linear S–V plot at higher pesticide concentrations
(inset of Fig. 5b). However, other pesticides exhibit trivial (Fig. S20, ESI†) corroborates the concurrent presence of static and
PL intensity changes (Fig. S19 and S20, ESI†), except for IPT, dynamic quenching and/or resonance energy transfer.68,69 From
which resulted in a turn-on response, with 1.1- and 1.5-fold linear fitting of the S–V plot in the concentration range of

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0–0.3 mM, KSV is calculated to be 3.88  104 M1. In addition, stress that we also performed fast-response analyte tests with
using 10 mM dichloran, the LOD value turned out to be 124 nM other pesticides, but negligible responses were obtained in
(60 ppb). Of note is that present KSV value ranks as one of the every case. The performance of 8a is summarized in Table 1.
highest among all dichloran-sensing MOFs, while the corres-
ponding LOD value is of true significance (Table S9, ESI†). Encour- Validation of the sensing mechanism
aged by such ultrasensitive detection of a nitro-moiety containing
dichloran pesticide, we evaluated the KEC value for IPT based on its The diverse degrees of PL intensity alterations in response
turn-on response (Fig. S20, ESI†). To our delight, KEC is found to be to electronically and structurally different organo-toxins with
1.82  103 M1, while the LOD value is 226 nM (110 ppb). profound nonlinearity in the S–V plots suggest the presence of
resonance energy transfer (RET) and photoinduced electron
transfer (PET) in the sensing mechanism.22,70 Based on the
Multicyclic, anti-interfering and fast-responsive pesticide PXRD patterns (Fig. S17 and S26, ESI†) of individual MOF
detection samples after multiple sensing-recovery cycles exhibiting the
The regenerative features of 8a were verified via recovering the complete retention of structural integrity in all cases, structural
MOF after each sensing experiment through centrifugation, alteration/decomposition could be ignored. Alternatively, inter-
followed by washing with fresh solvent (DCM), and vacuum drying. actions between aminophenols and/or pesticides are considered
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The PXRD pattern of regenerated 8a showed the complete main- superficial as (a) the channel apertures in the four-fold inter-
taining of the structural integrity (Fig. S26, ESI†). A dispersed penetrated structures do not allow the pore-based encapsulation
solution of the recovered framework successfully revealed the full of large-sized organo-aromatics and (b) the considerable alterations
recurrence of the pristine PL intensity. Furthermore, the expected in the PL intensities (Fig. 5d and Fig. S18, S27, ESI†) occur within
turn-on or turn-off emission attributes in the presence of dichloran 20 s (vide supra), meaning that the probe material can hardly adsorb
or IPT were maintained for up to five consecutive sensing-recovery any analyte in the initial stages.71 Given that dichloran involves an
cycles (Fig. S25, ESI†). Subsequently, anti-interference studies were electron-deficient nitro group, the expected turn-off response may
carried out as per the aforementioned protocol. arise from a RET process, which is a measure of effective energy
The emission response was measured via adding 60 mL of transfer between the fluorophore and the analyte, which can be
interfering pesticide (5 mM) to a blank MOF dispersion, which quantified based on the extent of the overlap between the
caused insignificant changes in the PL intensity (Fig. S23 and absorption band of the non-emissive analyte and the emission
S24, ESI†). In sharp contrast, the addition of the same amount band of 8a.72 As depicted in Fig. 6, the absorption spectrum of
of dichloran instigates (Fig. 5f) drastic quenching of each of dichloran shows the largest effective overlap with the emission
these mixed suspensions (MOF + interfering pesticide). This spectrum of 8a, whilst this spectral overlap is somewhat lower in
process was continued once more, and the outcomes clearly the case of 7a. This observation clearly verifies the relatively
show that the framework is an outstanding probe for selectively higher degree of quenching in the case of 8a than 7a. Likewise,
detecting dichloran. The ability of 8a for the discriminating the maximum overlap of the emission spectrum of 8a ensues
detection of IPT in the presence of other interferents was with the absorption spectrum of 4-AP, implying that RET plays a
examined via a similar CAT protocol,26,36 divulging its excellent key role in the fluorescence quenching performance. Then again,
selective recognition through the enhancement of the optical competition for excitation absorption due to intermolecular energy
signal (Fig. S24, ESI†). We next pursued the percentage changes transfer between the studied analytes and the individual MOF
in the optical response of 8a toward these organo-toxins with cannot be discarded. In fact, the UV-vis absorption spectra of all
respect to time (vide supra). Within 20 s, the addition of 40 mL of the studied organo-aromatics (Fig. S28, ESI†) show absorption
dichloran resulted in a B63% decrease in the PL intensity bands in the range of 250–500 nm, covering the entire excitation
(Fig. 5d). On the other hand, the optical signal of a separate wavelength range of 8a. Clearly, the excitation light would be
MOF dispersion experiences a 1.2-fold increase in emission absorbed by solutions of dichloran and/or 4-AP to instigate a
(Fig. S27, ESI†) upon adding 40 mL of IPT. Under these static turn-off response to this framework.
experimental conditions, the fluorescence emission intensity However, it is surprising to note that neither DEP nor IPT,
was recorded (at regular time intervals of 20 s) for a total time which demonstrate major fluorescence enhancement, shows any
span of 120 s, and no more changes were observed in either of spectral overlap. This fact leads us to postulate that RET is not the
the cases. These observations demonstrate the ultra-fast sole factor behind their noteworthy turn-on responses. Alternatively,
response toward both studied pesticides. It is imperative to the mechanism behind the turn-on optical response may be

Table 1 The performance characteristics of 8a for the detection of DEP, IPT, and DCNA

Analyte DEP IPT DCNA

Sensing mode Turn-on Turn-on Turn-off
Enhancement/quenching extent (fold/%) 17.7-fold 1.5-fold 99.5%
KSV/KEC (M1) 3.74  105 1.82  103 3.88  104
Response time (mL s1) 40 mL/20 s 40 mL/20 s 40 mL/20 s
LOD (nanomolar) 79.8 nM 226 nM 124 nM

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Fig. 6 Overlap between the absorbance spectra of (a) aminophenols and (b) pesticides with the emission spectra of 7a and 8a.
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related to a PET effect.65,73,74 Both 7a and 8a, encompassing the individual selected analytes and functional struts in both of the
organic ligands in highly connected network structures, can be MOFs. Of note is that additional interactions involving the acces-
visualized as giant ‘‘molecules’’, involving definite energy gaps sible N-atoms of the triazole rings and each of the selected organo-
between the valence band (VB) and conduction band (CB). In toxins can be perceived in the case of 8a, corroborating its superior
principle, the CBs of 7a and 8a reside at energy levels lower than fluoro-sensing aptitude compared to 7a.
the lowest unoccupied molecular orbitals (LUMOs) of electron-
rich organo-aromatics. In this environment, luminescence Conclusions
enhancement occurs from the transfer of electrons from the
aforementioned LUMOs to the CB of the MOF upon excitation. In conclusion, a pair of diamondoid Cd(II) frameworks, viz.
Generally, a PET mechanism in the majority of sensory MOFs is CSMCRI-7 and CSMCRI-8, are used that share identical structures
simply supported by highest occupied molecular orbital (HOMO)– and pore apertures but differ in functionality. As a consequence
LUMO energy calculations based on the analyte and ligand of accessible N-atom-decorated pore surfaces, the CO2 uptake
components,37 which does not allow the exact scenario to be capacity and selectivity are increased two-fold in activated
revealed in an extended MOF structure. We strived to calculate CSMCRI-8 with a large upsurge in the adsorption enthalpy
the HOMOs and LUMOs of 8a and 7a along with all amino- compared to the unfunctionalized analogue. Such an unusual
phenols and pesticides through comprehensive periodic density variation in sorption behavior is rationalized based on grand
functional theory (periodic-DFT) calculations (Fig. 7), using a canonical Monte Carlo simulation that portray distinguished
mixed Gaussian plane wave scheme, implemented in the CP2K microscopic CO2 adsorption mechanisms in these isostructural
package75 with Grimme’s D3 dispersion corrections76 (a detailed MOFs, and the results clearly depict stronger interactions
description of the periodic-DFT method is provided in the ESI†). between CO2 molecules and free N-atoms inside the pore walls.
The results portray (Fig. 7) that the LUMO energy levels of 8a Subsequently, luminescence detection studies involving lethal
(1.37 eV) and 7a (1.35 eV) are higher than the LUMO of organo-aromatics, including toxic amino-phenols and lethal
dichloran (DCNA) (1.83 eV), assisting smooth electron transfer pesticides, reveal major alterations in sensing aptitude as a
to this pesticide and supporting high quenching efficiencies. result of pore functionalization, which induces stronger host–
Conversely, the LUMOs of DEP (0.60 eV) and IPT (0.90 eV) guest interactions. Notably, both frameworks deliver the first-
reside at higher energy levels than the LUMOs of 8a (1.37 eV) ever example of the recyclable and nanomolar-level detection of
and 7a (1.35 eV), which results in smooth electron transfer toxic 3-(diethylamino)phenol and the lethal pesticide isopro-
from the LUMOs of these analytes to the LUMOs of LMOFs, turon via a remarkable turn-on response, and guest-responsive
causing emission enhancement. To gain additional insight into fluorescence modulation is obtained in the significant turn-off
the PET mechanism, we extended the DFT calculations to study sensing of the pesticide dichloran. In addition to a battery
modifications in the HOMO–LUMO energies of MOFs in the of experimental evidence, periodic-density functional theory
presence of individual analytes (DCNA, DEP, and IPT). As calculations validate the superior framework–analyte inter-
divulged in Fig. S7 (ESI†), substantial drops in the energy gaps of actions in the pore-engineered structure and portray the unique
8a are evidenced upon interaction with DCNA (1.30 eV - 0.77 eV), redistribution of molecular orbital energy levels in the diamondoid
DEP (1.30 eV - 1.26 eV), and IPT (1.30 eV - 1.25 eV), further networks in response to individual organo-toxins. Given that
validating the facile electron transfer process. To acquire atomistic- significant attention is focused on the development of multi-
level insights into sensing and substantiate the marked emission functional materials for environmental remediation, this work
differences between 7a and 8a towards the studied analytes, highlights the obvious impact of pore functionalization on the
geometry optimization of MOF@analyte complexes was carried substantial development of performance characteristics, and it
out. As illustrated in Fig. 7g, strong intermolecular H-bonding, sheds light on the tailor-made fabrication of advanced systems
C–H  p interactions, and p  p stacking interactions exist between for targeted applications.

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Fig. 7 The HOMO–LUMO energy levels of 7a, 8a, and individual analytes, with the redistribution of HOMO–LUMO energy gaps for 7a and 8a in the
presence of DEP (a and b), dichloran (DCNA) (c and d), and IPT (e and f), demonstrating luminescence quenching (for DCNA) and enhancement (for DEP
and IPT) effects. (g) The geometry optimized structures of 7a and 8a with DEP, DCNA, and IPT molecules, showing superior non-covalent interactions in
the cases of the pore-engineered MOF.

Experimental section (HL1) (37.23 mg, 0.19 mmol) was dissolved in N,N-dimethyl-
Synthesis of 4-(1H-imidazol-1-yl)benzoic acid (HL1) formamide (DMF; 7 mL), sealed in 15 mL glass vial, and heated
at 120 1C for 2 days.45 The colourless, rectangular crystals were
The ligand was synthesised and characterised via our previously isolated (Scheme S1, ESI†) in 65% yield.
reported method, replacing the equivalent amount of triazole Anal. calcd for C26H28CdN6O6 = [Cd(L1)2]2DMF: C, 49.34; H,
with imidazole.49 4.46; N, 13.28%; found: C, 48.36; H, 4.59; N, 13.53%. FT-IR
(KBr) analysis: 1246, 1301, 1392, 1492, 1521, 1554, 1611, 1668,
Synthesis of 4-(1H-1,2,4-triazol-1-yl)benzoic acid (HL2) 3382 cm1 (Fig. S2, ESI†).
The ligand was synthesised and characterised via our previously Synthesis of CSMCRI-8. A mixture of Cd(NO3)24H2O (48.4 mg,
reported method.36 0.156 mmol) and 4-(1H-1,2,4-triazol-1-yl)benzoic acid (HL2)
Synthesis of CSMCRI-7. A mixture of Cd(NO3)24H2O (37.23 mg, 0.19 mmol) was dissolved in N,N-dimethylformamide
(48.4 mg, 0.156 mmol) and 4-(1H-imidazol-1-yl)benzoic acid (DMF; 7 mL), sealed in 15 mL glass vial, and heated at 120 1C

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Journal of Materials Chemistry C Paper

for 2 days.46 The colourless, rectangular crystals were isolated 11 M. Asif, M. Suleman, I. Haq and S. A. Jamal, Greenhouse
(Scheme S1, ESI†) in 65% yield. Gases Sci. Technol., 2018, 8, 998–1031.
Anal. calcd for C24H26CdN8O6 = [Cd(L2)2]2DMF: C, 45.40; H, 12 H.-M. Wen, C. Liao, L. Li, A. Alsalme, Z. Alothman,
4.13; N, 17.65%; found: C, 46.15; H, 4.07; N, 17.91%. FT-IR R. Krishna, H. Wu, W. Zhou, J. Hu and B. Chen, J. Mater.
(KBr) analysis: 1279, 1379, 1556, 370, 1525, 1568, 1605, 1685, Chem. A, 2019, 7, 3128–3134.
3247 cm1 (Fig. S2, ESI†). 13 X.-Y. Li, L.-N. Ma, Y. Liu, L. Hou, Y.-Y. Wang and Z. Zhu, ACS
Synthesis of 7a and 8a. As-synthesised crystals were washed Appl. Mater. Interfaces, 2018, 10, 10965–10973.
with fresh DMF and then dried in air. The guest solvent mole- 14 Y.-Z. Li, H.-H. Wang, H.-Y. Yang, L. Hou, Y.-Y. Wang and
cules in the frameworks were exchanged with dichloromethane Z. Zhu, Chem. – Eur. J., 2018, 24, 865–871.
via soaking the crystals in DCM for two days, followed by 15 N. Xu, Q. Zhang, B. Hou, Q. Cheng and G. Zhang, Inorg.
exchanging the solvent 3 times a day. The crystals were dried Chem., 2018, 57, 13330–13340.
overnight under vacuum at 120 1C to generate the solvent-free 16 M.-L. Hu, S. A. A. Razavi, M. Piroozzadeh and A. Morsali,
frameworks 7a and 8a. Inorg. Chem. Front., 2020, 7, 1598–1632.
17 F. Bigdeli, F. Rouhani, A. Morsali and A. Ramazani, Ultrason.
Sonochem., 2020, 62, 104862.
Conflicts of interest
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18 C. Ma, T. Bian, S. Yang, C. Liu, T. Zhang, J. Yang, Y. Li, J. Li,

R. Yang and W. Tan, Anal. Chem., 2014, 86, 6508–6515.
The authors declare no conflicts of interest.
19 C. Liu, L. Zhou, F. Wei, L. Li, S. Zhao, P. Gong, L. Cai and
K. M.-C. Wong, ACS Appl. Mater. Interfaces, 2019, 11, 8797–8806.
Acknowledgements 20 J.-C. Yang, Y.-C. Ho and Y.-H. Chan, ACS Appl. Mater.
Interfaces, 2019, 11, 29341–29349.
S. N. acknowledges DST-SERB (Grant No. ECR/2016/000156) and 21 D. K. Singha, P. Majee, S. Mandal, S. K. Mondal and P. Mahata,
CSIR (Grant No. MLP-0028). M. S. acknowledges UGC, Delhi, for Inorg. Chem., 2018, 57, 12155–12165.
providing a senior research fellowship. Analytical support from 22 N. Xu, Q. Zhang and G. Zhang, Dalton Trans., 2019, 48,
AESD & CIF (CSMCRI) and crystallographic help from Dr 2683–2691.
E. Suresh are gratefully acknowledged. R. S. P. gratefully 23 R. Mehta, H. Brahmbhatt, N. K. Saha and A. Bhattacharya,
acknowledges SERB (SRG/2019/000912), the Department of Desalination, 2015, 358, 69–75.
Science and Technology (DST), Govt. of India, for the award of 24 N. Seal, R. Goswami, M. Singh, R. S. Pillai and S. Neogi,
a Start-up Research Grant (SERB-SRG) with reference SRG/2019/ Inorg. Chem. Front., 2021, 8, 296–310.
000912 and thanks the SRM Supercomputer Center, SRMIST for 25 B. Parmar, Y. Rachuri, K. K. Bisht and E. Suresh, Inorg.
providing the computational facilities. A. S. P. thanks SRM Chem., 2017, 56, 10939–10949.
Institute of Science and Technology for providing PhD fellow- 26 G. Chakraborty, P. Das and S. K. Mandal, ACS Appl. Mater.
ship support. The CSMCRI communication number for this Interfaces, 2018, 10, 42406–42416.
publication is 67/2020. 27 D. Yue, D. Zhao, J. Zhang, L. Zhang, K. Jiang, X. Zhang,
Y. Cui, Y. Yang, B. Chen and G. Qian, Chem. Commun., 2017,
53, 11221–11224.
References
28 X. Zhang, Q. Hu, T. Xia, J. Zhang, Y. Yang, Y. Cui, B. Chen and
1 Z. Wang and S. M. Cohen, Chem. Soc. Rev., 2009, 38, 1315–1329. G. Qian, ACS Appl. Mater. Interfaces, 2016, 8, 32259–32265.
2 H. Furukawa, K. E. Cordova, M. O’Keeffe and O. M. Yaghi, 29 A. Mallick, A. M. El-Zohry, O. Shekhah, J. Yin, J. Jia, H. Aggarwal,
Science, 2013, 341, 1230444. A.-H. Emwas, O. F. Mohammed and M. Eddaoudi, J. Am. Chem.
3 J. Wu, F. Xu, S. Li, P. Ma, X. Zhang, Q. Liu, R. Fu and D. Wu, Soc., 2019, 141, 7245–7249.
Adv. Mater., 2019, 31, 1802922. 30 J. Dong, S.-L. Hou and B. Zhao, ACS Appl. Mater. Interfaces,
4 Y. Inubushi, S. Horike, T. Fukushima, G. Akiyama, R. Matsuda 2020, 12, 38124–38131.
and S. Kitagawa, Chem. Commun., 2010, 46, 9229–9231. 31 H. Li, K. Wang, D. Feng, Y.-P. Chen, W. Verdegaal and
5 P. Kanoo, R. Matsuda, H. Sato, L. Li, N. Hosono and S. Kitagawa, H.-C. Zhou, ChemSusChem, 2016, 9, 2832–2840.
Chem. – Eur. J., 2020, 26, 2148–2153. 32 L. Abylgazina, I. Senkovska, S. Ehrling, V. Bon, P. Petkov, J. D.
6 X.-G. Yang, X.-M. Lu, Z.-M. Zhai, Y. Zhao, X.-Y. Liu, L.-F. Ma Evans, S. Krylova, A. Krylov and S. Kaskel, CrystEngComm,
and S.-Q. Zang, Chem. Commun., 2019, 55, 11099–11102. 2021, 23, 538–549.
7 Y. Zhao, Y.-J. Wang, N. Wang, P. Zheng, H.-R. Fu, M.-L. Han, 33 J.-Q. Liu, Z.-D. Luo, Y. Pan, A. Kumar Singh, M. Trivedi and
L.-F. Ma and L.-Y. Wang, Inorg. Chem., 2019, 58, 12700–12706. A. Kumar, Coord. Chem. Rev., 2020, 406, 213145.
8 X.-G. Yang, Z.-M. Zhai, X.-M. Lu, Y. Zhao, X.-H. Chang and 34 M. Singh, P. Solanki, P. Patel, A. Mondal and S. Neogi, Inorg.
L.-F. Ma, Dalton Trans., 2019, 48, 10785–10789. Chem., 2019, 58, 8100–8110.
9 J.-R. Li, R. J. Kuppler and H.-C. Zhou, Chem. Soc. Rev., 2009, 35 R. Goswami, S. C. Mandal, B. Pathak and S. Neogi, ACS Appl.
38, 1477–1504. Mater. Interfaces, 2019, 11, 9042–9053.
10 H. He, J. A. Perman, G. Zhu and S. Ma, Small, 2016, 12, 36 M. Singh, S. Senthilkumar, S. Rajput and S. Neogi, Inorg.
6309–6324. Chem., 2020, 59, 3012–3025.

7152 | J. Mater. Chem. C, 2021, 9, 7142–7153 This journal is © The Royal Society of Chemistry 2021
 View Article Online

Paper Journal of Materials Chemistry C

37 N. Seal, M. Singh, S. Das, R. Goswami, B. Pathak and 59 W. P. Lustig, S. Mukherjee, N. D. Rudd, A. V. Desai, J. Li and
S. Neogi, Mater. Chem. Front., 2021, 5, 979–994. S. K. Ghosh, Chem. Soc. Rev., 2017, 46, 3242–3285.
38 F. ZareKarizi, M. Joharian and A. Morsali, J. Mater. Chem. A, 60 L. Luo, P. Wang, G.-C. Xu, Q. Liu, K. Chen, Y. Lu, Y. Zhao
2018, 6, 19288–19329. and W.-Y. Sun, Cryst. Growth Des., 2012, 12, 2634–2645.
39 Y.-Z. Li, Y. Liu, Y.-K. Lu, L.-N. Ma, L. Hou and Y.-Y. Wang, 61 X.-Y. Wan, F.-L. Jiang, L. Chen, J. Pan, K. Zhou, K.-Z. Su,
Chem. – Asian J., 2019, 14, 2988–2994. J.-D. Pang, G.-X. Lyu and M.-C. Hong, CrystEngComm, 2015,
40 N. Gcwensa and C. L. Oliver, Inorg. Chem., 2020, 59, 17, 3829–3837.
13211–13222. 62 X.-J. Hong, Q. Wei, Y.-P. Cai, S.-R. Zheng, Y. Yu, Y.-Z. Fan,
41 A. Dutta, A. Singh, X. Wang, A. Kumar and J. Liu, CrystEng- X.-Y. Xu and L.-P. Si, ACS Appl. Mater. Interfaces, 2017, 9,
Comm, 2020, 22, 7736–7781. 4701–4708.
42 Q. Zhang, J. Wang, A. M. Kirillov, W. Dou, C. Xu, C. Xu, 63 M. Wang, L. Guo and D. Cao, Anal. Chem., 2018, 90, 3608–3614.
L. Yang, R. Fang and W. Liu, ACS Appl. Mater. Interfaces, 64 B. Wang, Q. Yang, C. Guo, Y. Sun, L.-H. Xie and J.-R. Li, ACS
2018, 10, 23976–23986. Appl. Mater. Interfaces, 2017, 9, 10286–10295.
43 L. Li, J. Cheng, Z. Liu, L. Song, Y. You, X. Zhou and W. Huang, 65 R. Goswami, S. C. Mandal, N. Seal, B. Pathak and S. Neogi,
ACS Appl. Mater. Interfaces, 2018, 10, 44109–44115. J. Mater. Chem. A, 2019, 7, 19471–19484.
Published on 07 May 2021. Downloaded on 8/11/2021 8:51:48 PM.

44 H. Cui, Y. Ye, T. Liu, Z. A. Alothman, O. Alduhaish, R.-B. Lin 66 K. Vikrant, D. C. W. Tsang, N. Raza, B. S. Giri, D. Kukkar and
and B. Chen, Inorg. Chem., 2020, 59, 17143–17148. K.-H. Kim, ACS Appl. Mater. Interfaces, 2018, 10, 8797–8817.
45 A. Aijaz, E. Barea and P. K. Bharadwaj, Cryst. Growth Des., 67 H.-H. Yu, J.-Q. Chi, Z.-M. Su, X. Li, J. Sun, C. Zhou, X.-L. Hu
2009, 9, 4480–4486. and Q. Liu, CrystEngComm, 2020, 22, 3638–3643.
46 T. Li, X. Liu, Z.-P. Huang, Q. Lin, C.-L. Lin, Q.-G. Zhan, X.-D. 68 Y. Rachuri, B. Parmar and E. Suresh, Cryst. Growth Des.,
Xu and Y.-P. Cai, Inorg. Chem. Commun., 2014, 39, 70–74. 2018, 18, 3062–3072.
47 J. P. Perdew, K. Burke and M. Ernzerhof, Phys. Rev. Lett., 69 B. Parmar, K. K. Bisht, Y. Rachuri and E. Suresh, Inorg.
1996, 77, 3865–3868. Chem. Front., 2020, 7, 1082–1107.
48 Y.-B. Men, J. Sun, Z.-T. Huang and Q.-Y. Zheng, CrystEng- 70 C.-L. Tao, B. Chen, X.-G. Liu, L.-J. Zhou, X.-L. Zhu, J. Cao,
Comm, 2009, 11, 978–979. Z.-G. Gu, Z. Zhao, L. Shen and B. Z. Tang, Chem. Commun.,
49 S. Senthilkumar, R. Goswami, V. J. Smith, H. C. Bajaj and 2017, 53, 9975–9978.
S. Neogi, ACS Sustainable Chem. Eng., 2018, 6, 10295–10306. 71 S. W. Thomas, G. D. Joly and T. M. Swager, Chem. Rev., 2007,
50 A. Spek, J. Appl. Crystallogr., 2003, 36, 7–13. 107, 1339–1386.
51 N. Sikdar, A. Hazra and T. K. Maji, Inorg. Chem., 2014, 53, 72 N. Xu, Q. Zhang, B. Hou, Q. Cheng and G. Zhang, Inorg.
5993–6002. Chem., 2018, 57, 13330–13340.
52 P. Kanoo, R. Haldar, S. K. Reddy, A. Hazra, S. Bonakala, 73 M. D. Allendorf, C. A. Bauer, R. K. Bhakta and R. J. T. Houk,
R. Matsuda, S. Kitagawa, S. Balasubramanian and T. K. Chem. Soc. Rev., 2009, 38, 1330–1352.
Maji, Chem. – Eur. J., 2016, 22, 15864–15873. 74 C.-X. Yao, N. Zhao, J.-C. Liu, L.-J. Chen, J.-M. Liu, G.-Z. Fang
53 R. Goswami, N. Seal, S. R. Dash, A. Tyagi and S. Neogi, ACS and S. Wang, Polymers, 2020, 12, 691.
Appl. Mater. Interfaces, 2019, 11, 40134–40150. 75 T. D. Kühne, M. Iannuzzi, M. D. Ben, V. V. Rybkin, P. Seewald,
54 A. Pal, S. Chand, J. C. Boquera, F. Lloret, J.-B. Lin, S. C. Pal F. Stein, T. Laino, R. Z. Khaliullin, O. Schütt, F. Schiffmann,
and M. C. Das, Inorg. Chem., 2019, 58, 6246–6256. D. Golze, J. Wilhelm, S. Chulkov, M. H. Bani-Hashemian,
55 C. Song, J. Hu, Y. Ling, Y. Feng, R. Krishna, D.-l. Chen and V. Weber, U. Borštnik, M. Taillefumier, A. S. Jakobovits,
Y. He, J. Mater. Chem. A, 2015, 3, 19417–19426. A. Lazzaro, H. Pabst, T. Müller, R. Schade, M. Guidon,
56 X. Wang, M. Chen and M. Du, Inorg. Chem., 2016, 55, S. Andermatt, N. Holmberg, G. K. Schenter, A. Hehn, A. Bussy,
6352–6354. F. Belleflamme, G. Tabacchi, A. Glöß, M. Lass, I. Bethune,
57 A. Chakraborty, A. Achari, M. Eswaramoorthy and T. K. C. J. Mundy, C. Plessl, M. Watkins, J. VandeVondele, M. Krack
Maji, Chem. Commun., 2016, 52, 11378–11381. and J. Hutter, J. Chem. Phys., 2020, 152, 194103–194150.
58 S. S. Dhankhar and C. M. Nagaraja, New J. Chem., 2019, 43, 76 S. Grimme, J. Antony, S. Ehrlich and H. Krieg, J. Chem. Phys.,
2163–2170. 2010, 132, 154104.

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