Journal of Molecular Liquids 345 (2022) 118242

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Adsorption behavior and solvent effects of an adamantane-triazole

derivative on metal clusters – DFT simulation studies
Jamelah S. Al-Otaibi a, Y. Sheena Mary b,⇑, Y. Shyma Mary b, Zakir Ullah c, Hyung Wook Kwon c,⇑
a
Department of Chemistry, College of Science, Princess Nourah bint Abdulrahman University, Saudi Arabia
b
Thushara, Neethinagar-64, Kollam, Kerala, India
c
Convergence Research Center for Inset Vectors, Division of Life Sciences, College of Life Sciences and Bioengineering, Incheon National University, Songdo-don, Incheon 22012,
South Korea

a r t i c l e i n f o a b s t r a c t

Article history: Adsorption of 3-(adamantan-1-yl)-4-phenyl-1-[(4-phenylpiperazin-yl)methyl]-1H-1,2,4-triazole-5(4H)-

Received 6 October 2021 thione (APT) with metal clusters are reported theoretically. APT is found to form stable cluster with cop-
Revised 7 November 2021 per, silver and gold. APT-cluster complexation energy is more for gold complex. The calculated solvation
Accepted 27 November 2021
free energies are high for APT-Au clusters in both acetonitrile and ethanol solvents. The drug-gold clus-
Available online 03 December 2021
ter’s dipole moment is found to be higher than that of other systems. Raman spectra show an enhance-
ment in all APT-metal clusters. Different spectroscopic, chemical and electronic properties are also
Keywords:
investigated. Wavefunction analysis of APT-Cu shows that there is a strong interaction of the copper clus-
DFT
Adamantane
ter with the APT at two positions, one with the sulfur (S) atom and second with the carbon of the benzene
Metal clusters aromatic ring.
SERS Ó 2021 Elsevier B.V. All rights reserved.

1. Introduction
Viral diseases are deadly and one of the leading causes of
human life around the world and they are increasing at an alarm-
ing rate, along with emergence of new viruses and mutations in the
genomes of those that already exist [1]. Because of the scarcity of
effective medications and fear of unknown, new viruses draw a
lot of attention [2,3]. As a result, the development of effective
antivirals that can be used against virus is critical; yet, discovery
of novel viral inhibitors will be the century’s challenge. Further-
more, constant antiviral pharmaceutical therapy has resulted in
the formation of resistance to known inhibitors as well as changes
in viruses, posing significant hurdles in the discovery of novel
active and selective inhibitors. The lack of effective medicines for
majority of viral illnesses, as well as the high cost of traditional
antiviral therapies, necessitates the development of novel antiviral
agents.
Many investigations have been conducted with triazole, which
are important for the development of new medicines [3,4]. Triazole
derivative’s unusually structure and electron-rich system allow
them to interact easily with a variety of receptors, resulting in a
wide range of biological activities [5]. Antibacterial, antifungal
⇑ Corresponding authors.
E-mail addresses: marysheena2018@rediffmail.com (Y.S. Mary), hwkwon@inu.
ac.kr (H.W. Kwon).
and anticancer properties are only a few of the interesting pharma-
cological properties of adamantane derivatives [5–8]. Bioisosteric
substitution of adamantane with lipophilic groups changes water
solubility of epoxide hydrolase inhibitors [9]. Adamantane deriva-
tives have been used as medicines with various biological activities
[10].
Metal organic frameworks have piqued researcher’s interest in
recent decades due to their potential applications in a variety of
domains, including medication administration and sensing
[11,12]. The first effective structural determination of the gold nan-
ocluster atomic structures led to advancements in understanding
the structure of the gold-ligand interface, the interactions in the
ligand layer, the organic surface and the principles that regulate
their electrical structure and optical responses [13,14]. This has
sparked research into nanoscale and macroscale gold [15], silver
[16], and copper [17] cluster assemblies that could have a wide
range of applications in biological sensing [18] and optoelectronics
[19]. The study of silver cluster’s linear and nonlinear optical prop-
erties in various local environments shows that they could be used
in chemical, biological and optical limiting applications [20,21].
Jiang et al. investigated the effect of solvent on the size controlled
synthesis of gold nanoclusters, finding that polar solvents result in
lower cluster sizes due to hydrogen bond interactions [22]. The
relaxation in phosphine-protected gold clusters is greatly affected
by solvation in alcoholic solvents, according to Zhou et al. [23].

https://doi.org/10.1016/j.molliq.2021.118242
0167-7322/Ó 2021 Elsevier B.V. All rights reserved.
J.S. Al-Otaibi, Y. Sheena Mary, Y. Shyma Mary et al.
Metal nanoclusters, particularly those of coinage groups, have
attracted considerable research interest in recent years due to
the availability of atomic-level precision via combined experimen-
tal and theoretical methods, allowing the mechanisms in a variety
of nano-catalysts and functional materials to be revealed [24]. In
general, metal clusters are stabilized and realized by a layer of
ligands or solvents around them [25,26]. The ligand around the
metal interacts with metal clusters in a conventional or non-
conventional manner, allowing the geometry, shape, and stoi-
chiometry to be tuned [27]. For various applications, the interac-
tion between biomolecules and metal nanoclusters has been
researched in more depth utilizing various computational and the-
oretical methodologies [28–31]. Coinage metals, Au, Ag and Cu
have a wide range of properties and are often utilized as catalysts
in heterogeneous catalysis reactions [32]. Copper nanoparticles
have gotten a lot of attention from the coinage metals community
because of their in expensive price and ability to be used as large
scale industrial catalyst [33]. Biomolecule interactions with nanos-
tructures are a popular issue in biological applications [34].
Nanoparticles differ from their bulk counterparts in a number of
ways. The size dependent features of nanomaterials give up new
opportunities in a range of sectors. Metal nanoparticles have
received a lot of technological scientific interest [35,36]. APT is
an adamantane-triazole hybrid compound with antibacterial and
anti-inflammatory properties [37] and DFT approach is used to
understand interaction metallic clusters and APT.
2. Methods
DFT method is used to find interaction of APT with Ag/Au/Cu
clusters (mC) with M06-2X/6-311++G(d,p) (drug)/LANL2DZ (met-
als) (Fig. 1a and 1b) [38–41]. The adsorption energy E = EAPT-
mC
EmC
EAPT, where EAPT-mC, EmC, EAPT are energies of APT-mC,
mC and APT [42,43]. Gausssum suite is used to generate DOS
[44]. The complexes of interest were studied using the solvation
model, conductor-like polarizable continuum model (CPCM) with
acetonitrile and ethanol as the solvents [45].
Fig. 1a. Optimized geometry of APT.
2
Journal of Molecular Liquids 345 (2022) 118242
3. Results and discussion
FMOs are all over the atoms for mCs and APT (Figs. 2a & 2b)
[46,47]. Energy gap values are 2.0710/1.0688/0.0631/0.0332 eV
for APT/APT-Ag/APT-Au/ APT-Cu (Table 1) and the energy gaps
are less than that of pristine mC systems and drug. APT-Ag/Cu
complexes had the highest/lowest values of Eg values and are the
least and most conductive ones. In the complexes, S atom is at a
distance of 2.7599/2.6427/2.4995 Å from Ag/Au/Cu clusters giving
the interaction.
The dipole moments are https://doi.org/10.1119/12.3244/7.
9744 Debye for APT-Ag/Au/Cu) while that of APT is 5.4810 Debye.
The dipole moments pristine metal clusters are nearly zero and
after adsorption with APT significant changes are observed
(Table 2). In order to determine the reactivity of all systems, the
chemical descriptors play an important role. The hardness of APT
reduced after adsorption, showing that the resultant complex
had a higher reactivity than pure metal clusters implying that
more APT molecules may be adsorbed. Softness increases as hard-
ness was lowered, showing that the reactivity of the complex
increased after adsorption [48–50]. The ability of a fragment to
take electrons is given by the electrophilicity index [51]. After
adsorption, electrophilicity values are high, with highest/lowest
(735.2565/29.1311) for APT-Cu/Ag while the value of APT is only
17.5467 eV.
Adsorption of APT on mCs changes chemical potential (Table 1)
and highest/least changes (1.6151/0.4483) belong to APT-Au/Ag. In
APT, FMOs are respectively over the triazole and phenyl ring
attached to the triazole ring. HOMO of the complexed form of
APT-mCs is over the mCs and on CS in the case of APT-Ag. LUMO
are over the phenyl rings of APT-Ag, Au cluster and phenyl ring
with piperazine of APT-Au and phenyl ring with piperazine for
APT-Cu. Binding energies are:
54.78/
100.54/
55.04 kJ/mol for
APT-Ag/Au/Cu and negative values imply chemisorption. The
APT-metal interactions produces new energy states near Fermi
level (Fig. 3), which decreases Eg. DEg are
1.0022/2.0079/2.0388 eV for APT-Ag/Au/Cu which results in signif-
J.S. Al-Otaibi, Y. Sheena Mary, Y. Shyma Mary et al. Journal of Molecular Liquids 345 (2022) 118242

Fig. 1b. Optimized geometries of (a) APT-Ag (b) APT-Au (c) APT-Cu.

Fig. 2a. HOMO-LUMO plots of metal clusters (a) Ag (b) Au (c) Cu.

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J.S. Al-Otaibi, Y. Sheena Mary, Y. Shyma Mary et al. Journal of Molecular Liquids 345 (2022) 118242

Fig. 2b. HOMO-LUMO plots of (a) APT (b) APT-Ag (c) APT-Au (d) APT-Cu.

Table 1
Chemical descriptors of APT and APT-mC complexes (all parameters in eV).

System EHOMO ELUMO Energy gap Hardness Chemical potential Electrophilicity index
Ag
6.2234
4.1067 2.1167 1.0584
5.1651 12.6029
Au
4.0125
3.2185 0.7940 0.3970
3.6155 16.4633
Cu
4.9657
4.2169 0.7488 0.3744
4.5913 28.1518
APT
7.0637
4.9927 2.0710 1.0355
6.0282 17.5467
APT-Ag
6.1143
5.0455 1.0688 0.5344
5.5799 29.1311
APT-Au
4.4446
4.3815 0.0631 0.0316
4.4131 308.1489
APT-Cu
4.9573
4.9241 0.0332 0.0166
4.9407 735.2565

Table 2
NLO parameters.
The calculated solvation free energies are
58.65/
105.75/
57.2
System Dipole moment Polarizability First order 6 and
58.59/
106.62/
57.17 kJ/mol with acetonitrile and etha-
(Debye) (a.u.) hyperpolarizability (a.u.) nol as solvents for APT-Ag/Au/Cu systems.
APT 5.4810 338.6190 537.0370 Sulfur atom and phenyl ring attached to the piperazine of APT
APT- 10.1119 646.4854 8515.3754 were primarily responsible for the reactive areas [62]. Electroneg-
Ag ative and positive areas are over S, phenyl ring and N, H, respec-
APT- 12.3244 613.8966 6860.2129
Au
tively. Ag and Cu clusters are electronegative for APT-mCs while
APT- 7.9744 585.1252 7569.1595 Au cluster is electropositive for APT-Au system. Atoms of all APT
Cu (-mCs) follows the same behaviour as in the case of APT. The same
nature is observed in the electrostatic potential contour in terms of
closed and open contours (Fig. 4 & Fig. 5). The APT’s reactive spaces
icant changes in electrical conductivity [52]. The results suggest are useful for analzying APT-protein interactions [63]. Polarizabil-
that all mCs are good adsorbents for APT. ityof APT-mC’s are higher than that of APT (Table 2). Hyperpolariz-
Solvents are important in chemistry because they change the ability values show very large enhancement in APT-mC systems in
molecular behavior by varying the interactions between solvent comparison with that of APT [64].
molecules and solute molecules [53,54]. Several methodologies Figs. 6a and 6b shows Raman frequency multiplication in APT-
have been created to explore the solvent effects in quantum mC‘s. Charges of APT atom’s changes after adsorption in metals
mechanical computations of electronic structure [55]. The impact clusters (Table 3). All the mC clusters are interacting thorough
of solvents on the structural and spectroscopic features of diverse APT through the atoms, S, N atoms, C10, C12, C54 and C57 which
chemical systems has also been investigated [56–60]. Solvation get support from Mulliken charges. The charge of S1 is
free energy is a critical parameter for a broad variety of physical
0.011705 in APT changes to 0.061949, 0.116396 and 0.073528
properties that determines many chemical and biological pro- in APT-Ag/Au/Cu systems due to interactions. Charges of N2, N3,
cesses. It refers to the free energy associated with the transfer of N5/N4, N6 decreases/increases in APT-mCs. Charges of C10, C12,
a molecule between gaseous and a solvent at a specific tempera- C54 and C57 also show variations due to complex formation. Thus
ture and pressure [61]. The solvation free energy is the difference a metal cluster-based sensor for APT detection could be made
between energies of molecule in the solvent and gaseous phase. using SERS [65–67].

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J.S. Al-Otaibi, Y. Sheena Mary, Y. Shyma Mary et al. Journal of Molecular Liquids 345 (2022) 118242

Fig. 3. DOS spectra of (a) APT (b) APT-Ag (c) APT-Au (d) APT-Cu.

Fig. 4. MEP plots of metal clusters (a) Ag (b) Au (c) Cu.

Fig. 7 depicts both the AIM and RDG analysis of the (a) APT–Ag
(b) APT–Au and (c) APT–Cu complexes. Numerical data for calcu-
lated BCP systems were performed according to Bader’s theory
[68], q and r2q for all studied DFT cases. Hydrogen bonding
according to AIM theory states that q and r2q must be in the range
0.002–0.04 a.u. and 0.020 to 0.139 a.u, correspondingly [69]. The
BCPs for APT–Ag, APT–Au, and APT–Cu interaction are considered
for central positions, it was observed that APT–Metals at BCP#1
has highest values of q and r2q for the for the APT–Ag and APT–
Au complexes, however in the case of APT–Cu the BCP#2 also

5
J.S. Al-Otaibi, Y. Sheena Mary, Y. Shyma Mary et al. Journal of Molecular Liquids 345 (2022) 118242

Fig. 5. MEP plots of (a) APT (b) APT-Ag (c) APT-Au (d) APT-Cu.

Fig. 6a. Theoretical Raman spectra of (a) APT (b) APT-Ag (c) APT-Au (d) APT-Cu in the range 1750–0 cm
1.

Fig. 6b. Theoretical Raman spectra of (a) APT (b) APT-Ag (c) APT-Au (d) APT-Cu in the range 350–2500 cm
1.

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J.S. Al-Otaibi, Y. Sheena Mary, Y. Shyma Mary et al. Journal of Molecular Liquids 345 (2022) 118242

Table 3
Mulliken charges.

Atom APT APT-Ag APT-Au APT-Cu

1S
0.011705 0.061949 0.116396 0.073528
2N
0.322449
0.311613
0.307394
0.306592
3N
0.018049
0.006233
0.004732
0.009833
4N
0.117169
0.124982
0.129625
0.123643
5N
0.070156
0.065452
0.067432
0.059924
6N
0.205608
0.215614
0.219362
0.209281
7C
0.275276
0.199362
0.155315
0.180413
8C 0.054698 0.039467 0.039718 0.040654
9C 0.444666 0.432657 0.438932 0.421318
10C
0.092876
0.052451
0.033813
0.023438
12C 0.024507 0.040634 0.045197 0.055470
14C 0.004770 0.004814 0.006721
0.002048
16C 0.024051 0.022393 0.023753 0.017617
18C
0.089588
0.079602
0.090457
0.084637
20C 0.379162 0.369956 0.369392 0.372607
21C
0.104581
0.100892
0.100852
0.099983
24C 0.116084 0.116470 0.117463 0.116216
26C
0.070312
0.067827
0.067223
0.068670
29C 0.108838 0.109904 0.109810 0.109596
31C
0.105813
0.102688
0.103804
0.101413
34C
0.067168
0.063769
0.062641
0.063741
37C 0.116268 0.119237 0.120901 0.117318
39C
0.069607
0.066035
0.065323
0.066019
42C
0.103603
0.089009
0.087285
0.079622
45C 0.099063 0.116731 0.117729 0.115559
48C 0.077181 0.097878 0.102721 0.100314
51C 0.051241 0.052913 0.053076 0.057732
54C 0.043212 0.068285 0.086800 0.069047
57C 0.081205 0.132637 0.172110 0.112901
60C 0.451486 0.460330 0.487068 0.464313
61C
0.163835
0.161463
0.173962
0.156616
63C
0.000290 0.007665 0.018606
0.001480
65C
0.038716
0.033298
0.024154
0.031878
67C
0.009051 0.009980 0.046416
0.008046
69C
0.140582
0.121563
0.116403
0.131477

shows strong interaction of the copper cluster with the APT at two
position, one with the sulfur (S) atom and second with the carbon
of the benzene aromatic ring. In the RDG the different colors of the
interaction surface displaying the strength of the interaction and
repulsion. The blue color stands for strong interaction and the
green or green–brown color display the moderate type on interac-
tion, while the red color displays repulsive forces or ring strain.
BCPs for APT–Metals at BCP#1 has highest values of q and r2q
for the for the APT–Ag and APT–Au complexes, however in the case
of APT–Cu the BCP#2 also shows strong interaction of the copper
cluster.
CRediT authorship contribution statement

Jamelah S.Al-Otaibi: Conceptualization, Methodology, Data

4. Conclusions
DFT studies of APT with various metal clusters of copper, gold
and silver reported. The reactivity parameters were used to predict
reactive sites in the molecule. Reactive regions were over S, phenyl
ring and N, H. Ag and Cu clusters are electronegative for APT-mCs
while Au cluster is electropositive for APT-Au system. The APT-
mC’s NLO activity and Raman frequencies show enhancement.
Binding energy is maximum for APT-Au cluster (
100.54 kJ/mol)
while for Ag and Cu clusters the values are nearly same (
54.78
and
55.04 kJ/mol) and the negative values imply chemisorption.
Changes in energy gap values for APT-Ag/Au/Cu clusters results
in significant changes in electrical conductivity which means all
the clusters are good adsorbents for APT. The solvation free energy
of APT-Au is high in comparison with the other two clusters. The
curation, software, Writing-original draft, validation. Y.Sheena
Mary: Conceptualization, Methodology, Data curation, Writing-
original draft, review and editing, validation. Y.Shyma Mary: Con-
ceptualization, Methodology, Data curation, Writing-original draft,
validation. Zakir Ullah: Conceptualization, Methodoly, Data cura-
tion, software, Writing-original draft, validation. Hyung Wook
Kwon: Conceptualization, Methodoly, Data curation, software,
writing –review and editing, validation.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.

7
J.S. Al-Otaibi, Y. Sheena Mary, Y. Shyma Mary et al.
Fig. 7. Reduced density gradient (RDG) iso-surfaces (green or green-brown, and blue color display Van der Waals interactions and AIM molecular graph indicates critical
points and bond paths (small brown points) of (a) APT-Ag (b) APT-Au (c) APT-Cu.
Acknowledgements
This research was funded by the Deanship of Scientific Research
at Princess Nourah bint Abdulrahman University through the Fast-
track Research Funding Program.
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