Journal of Molecular Liquids 345 (2022) 118242

Contents lists available at ScienceDirect

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

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. Journal of Molecular Liquids 345 (2022) 118242

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

Fig. 1a. Optimized geometry of APT.

2
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.

3
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].

4
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 0.002–0.04 a.u. and 0.020 to 0.139 a.u, correspondingly [69]. The
(b) APT–Au and (c) APT–Cu complexes. Numerical data for calcu- BCPs for APT–Ag, APT–Au, and APT–Cu interaction are considered
lated BCP systems were performed according to Bader’s theory for central positions, it was observed that APT–Metals at BCP#1
[68], q and r2q for all studied DFT cases. Hydrogen bonding has highest values of q and r2q for the for the APT–Ag and APT–
according to AIM theory states that q and r2q must be in the range 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.

6
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 BCPs for APT–Metals at BCP#1 has highest values of q and r2q
position, one with the sulfur (S) atom and second with the carbon for the for the APT–Ag and APT–Au complexes, however in the case
of the benzene aromatic ring. In the RDG the different colors of the of APT–Cu the BCP#2 also shows strong interaction of the copper
interaction surface displaying the strength of the interaction and cluster.
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. CRediT authorship contribution statement

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

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

7
J.S. Al-Otaibi, Y. Sheena Mary, Y. Shyma Mary et al. Journal of Molecular Liquids 345 (2022) 118242

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 triazole derivatives, J. Heterocycl. Chem. 57 (2020) 2010-2023. https://doi.org/

10.1002/jhet.3929
[6] V.H. Pam, T.P.D. Phan, D.C. Phan, B.D. Vu, Synthesis and bioactivity of
This research was funded by the Deanship of Scientific Research thiosemicarbazones containing adamantane skeletons, Molecules 25 (2020)
at Princess Nourah bint Abdulrahman University through the Fast- 324, https://doi.org/10.3390/molecles25020324.
[7] I. Stankova, K. Chuchkov, R. Chayrov, L. Mukova, A. Galabov, D. Marinkova, D.
track Research Funding Program. Danalev, Adamantane derivatives containing thiazole moiety: synthesis,
antiviral and antibacterial activity, Int. J. Pept. Res. Ther. 26 (2020) 1781-
1787. https://doi.org/10.1007/s10989-019-09983-4
Reference [8] X. Zhu, J. Sun, S. Wang, W. Bu, M. Yao, K. Gao, Y. Song, J. Zhao, C. Lu, E. Zhang,
Synthesis, crystal structure, superoxide scavenging activity, anticancer and
[1] S.A. El-Sebaey, Recent advances in1,2,4-triazole scaffolds as antiviral agents, docking studies of novel adamantly nitroxide derivatives, J. Mol. Struct. 1108
Chem. Select 5 (37) (2020) 11654–11680, https://doi.org/10.1002/ (2016) 611-617. https://doi.org/10.1016/j.molstruc.2015.12.048
slct.202002830. [9] Vladimir Burmistrov, Christophe Morisseau, Dmitry Karlov, Dmitry Pitushkin,
[2] W. Furuyama, A. Marzi, Ebola Virus: Pathogenesis and countermeasure Andrey Vernigora, Elena Rasskazova, Gennady M. Butov, Bruce D. Hammock,
development, Annu. Rev. Virol. 6 (2019) 435-458. https://doi.org/10.1146/ Bioisosteric substitution of adamantane with bicyclic lipophilic groups
annurev-viorology-092818-015708 improves water solubility of human soluble epoxide hydrolase inhibitors,
[3] D. Musso, A.I. Ko, D. Baud, Zika virus infection-After the pandemic, N. Engl. J. Bioorg. Med. Chem. Lett. 30 (18) (2020) 127430, https://doi.org/10.1016/j.
Med. 381 (2019) 1444-1457. https://doi.org/10.1056/NEJMra1808246 bmcl.2020.127430.
[4] R. Kharb, M.S. Yar, P.C. Sharma, Recent advances and future perspectives of [10] V.M. Dembitsky, T.A. Gloriozova, V.V. Poroikov, Pharmacological profile of
triazole analogs as promising antiviral agents, Mini-Rev. Med. Chem. 11 (2010) natural and synthetic compounds with adamantane-based scaffolds as
84-96. https://doi.org/10.2174/13895571193564051 potential agents for the treatment of neurodegenerative diseases, Biochem.
[5] G. Khan, S. Sreenivasa, S. Govindaiah, V. Chandramohan, P.R. Shetty, Synthesis, Biophys. Res. Commun. 529 (2020) 1225–1241, https://doi.org/10.1016/j.
biological screening, in silico study and fingerprint applications of novel 1,2,4- bbrc.2020.06.123.

8
J.S. Al-Otaibi, Y. Sheena Mary, Y. Shyma Mary et al. Journal of Molecular Liquids 345 (2022) 118242

[11] P. Horcajada, T. Chalati, C. Serre, B. Gillet, C. Sebrie, T. Baati, J.F. Eubank, D. [34] S. Pramanik, S. Chatterjee, A. Saha, P.S. Devi, G.S. Kumar, Unravelling the
Heurtaux, P. Clayette, C. Kreuz, J.S. Chang, Y.K. Hwang, V. Marsaud, P.N. Bories, interaction of silver nanoparticles with mammalian and bacterial DNA, J. Phys.
L. Cynober, S. Gil, G. Ferey, P. Couvreur, R. Gref, Porous metal organic frame Chem. B 120 (2016) 5313-5324. https://doi.org/10.1021/acs.jpcb.6b01586
work nanoscale carriers as a potential platform for drug delivery and imaging, [35] M.C. Shukla, M. Dubey, E. Zakar, J. Leszczynski, DFT investigation of the
Nat. Mater. 9 (2010) 172–178, https://doi.org/10.1038/nmat2608. interaction of gold nanoclusters with nucleic acid base guanine and the
[12] Xiao-Min Kang, Han-Shi Hu, Zhi-Lei Wu, Jia-Qi Wang, Peng Cheng, Jun Li, Bin Watson-Crick guanine-cytosince base pair, J. Phys. Chem. C 113 (2009) 3960-
Zhao, An ultrastablematryoshka [Hf13] nanocluster as a luminescent sensor 3966. https://doi.org/10.1021/jp808622y
for concentrated alkali and acid, Angew. Chem. Int. Ed. 58 (46) (2019) 16610– [36] Lucas Freitas de Freitas, Gustavo Varca, Jorge dos Santos Batista, Ademar
16616, https://doi.org/10.1002/anie.201907557. Benévolo Lugão, An overview of the synthesis of gold nanoparticles using
[13] Hannu Häkkinen, The gold-sulfur interface at the nanoscale, Nat. Chem. 4 (6) radiation technologies, Nanomaterials 8 (11) (2018) 939, https://doi.org/
(2012) 443–455, https://doi.org/10.1038/nchem.1352. 10.3390/nano8110939.
[14] Jaakko Akola, Michael Walter, Robert L. Whetten, Hannu Häkkinen, Henrik [37] E.S. Al-Abdullah, H.H. Asiri, S. Lahsasni, E.E. Habib, T.M. Ibrahim, A.A. El-Emam,
Grönbeck, On the structure of thiolate-protected Au25, J. Am. Chem. Soc. 130 Synthesis, antimicrobial, and anti-inflammatory activity, of novel S-
(12) (2008) 3756–3757, https://doi.org/ substituted and N-substituted 5-(1-adamantyl)-1,2,4-triazole-3-thiols, Drug
10.1021/ja800594p10.1021/ja800594p.s002. Des. Dev. Ther. 8 (2014) 505–518, https://doi.org/10.2147/DDDT.S62465.
[15] Q. Li, J.C. Russell, T.-Y. Luo, X. Roy, N.L. Rosi, Y. Zhu, R. Jin, Modulating the [38] Gaussian 09, Revision C.01, M.J. Frisch, G.W. Trucks, H.B. Schlegel, G.E.
hierarchical fibrous assembly of Au nanoparticles with atomic precision, Nat. Scuseria, M.A. Robb, J.R. Cheeseman, G. Scalmani, V. Barone, B. Mennucci, G.A.
Commun. 9 (2018) 3871, https://doi.org/10.1038/s41467-018-06395-8. Petersson, H. Nakatsuji, M. Caricato, X. Li, H.P. Hratchian, A.F. Izmaylov, J.
[16] Mohammad J. Alhilaly, Ren-Wu Huang, Rounak Naphade, Badriah Alamer, Bloino, G. Zheng, J.L. Sonneberg, M. Hada, M. Ehara, K. Toyota, R. Fukuda, J.
Mohamed Nejib Hedhili, Abdul-Hamid Emwas, Partha Maity, Jun Yin, Hasegawa, M. Ishida, T. Nakajima, Y. Honda, O. Kitao, H. Nakai, T. Vreven, J.A.
Aleksander Shkurenko, Omar F. Mohammed, Mohamed Eddaoudi, Osman M. Montgomery, J.E. Peralta, F. Ogliaro, M. Bearpark, J.J. Heyd, E. Brothers, K.N.
Bakr, Assembly of atomically precise silver nanoclusters into nanocluster- Kudin, V.N. Staroverov, T. Keith, R. Kobayashi, J. Normand, K. Raghavachari, A.
based frameworks, J. Am. Chem. Soc. 141 (24) (2019) 9585–9592, https://doi. Rendell, J.C. Knox, J.B. Cross, V. Bakken, C. Adamo, J. Jaramillo, R. Gomperts, R.E.
org/10.1021/jacs.9b0248610.1021/jacs.9b02486.s00110.1021/jacs.9b02486. Stratmann, O. Yazyev, A.J. Austin, R. Cammi, C. Pomelli, J.W. Ochterski, R.L.
s00210.1021/jacs.9b02486.s00310.1021/jacs.9b02486.s004. Martin, K. Morokuma, V.G. Zakrzewski, G.A.Voth, P. Salvador, J.J. Dannenberg,
[17] Yi Liu, Dong Yao, Hao Zhang, Self-assembly driven aggregation-induced S. Dapprich, A.D. Daniels, O. Farkas, J.B. Foresman, J.V. Ortiz, J. Cioslowski, D.J.
emission of copper nanoclusters: a novel technology for lighting, ACS Appl. Fox, Gaussian Inc., Wallingford CT, 2010.
Mater. Interfaces 10 (15) (2018) 12071–12080, https://doi.org/10.1021/ [39] J.B. Foresman, A Guide to Using Gaussian, Pittsburg, PA, in: E: Frisch (Ed.),
acsami.7b13940. Exploring Chemistry with Electronic Structure Methods, 1996.
[18] Xiao-Hui Wu, Peng Luo, Zhong Wei, Yuan-Yuan Li, Ren-Wu Huang, Xi-Yan [40] R. Dennington, T. Keith, J. Millam, Gaussview, Version 5, Semichem Inc.,
Dong, Kai Li, Shuang-Quan Zang, Ben Zhong Tang, Guest-triggered Shawnee Missions KS, 2009.
aggregation-induced emission in silver chalcogenolate cluster metal-organic [41] Zakir Ullah, Renjith Thomas, Markovnikov versus anti-Markovnikov addition
frameworks, Adv. Sci. 6 (2) (2019) 1801304, https://doi.org/10.1002/ and C-H activation: pd-Cu synergistic catalysis, Appl. Organomet. Chem. 35 (1)
advs.201801304. (2021), https://doi.org/10.1002/aoc.v35.110.1002/aoc.6077.
[19] M. Galchenko, A. Black, L. Heymann, C. Klinke, Field effect and [42] Aljawhara H. Almuqrin, Jamelah S. Al-Otaibi, Y. Sheena Mary, Y. Shyma Mary,
photoconduction in Au25 nanoclusters filmds, Adv. Mater. 31 (2019), Renjith Thomas, Structural study of letrozole and metronidazole and
https://doi.org/10.1002/adma.201900684 e1900684. formation of self-assembly with graphene and fullerene with the
[20] I. Diez, M.I. Kanyuk, A.P. Demchenko, A. Walther, H. Jian, O. Ikkalaa, R.H.A. Ras, enhancement of physical, chemical and biological activities, J. Biomol. Struct.
Blue, green and red emissive silver nanoclusters formed in organic solvents, Dyn. 39 (15) (2021) 5509–5515, https://doi.org/10.1080/
Nanoscale 4 (2012) 4434–4437, https://doi.org/10.1039/C2NR30642E. 07391102.2020.1790420.
[21] K.B. Bhavitha, A.K. Nair, S. Perumbilavil, S. Joseph, M.S. Kala, A. Saha, A.R. [43] J.S. Al-Otaibi, Y.S. Mary, R. Thomas, S. Kaya, Detailed electronic structure,
Narayanan, N. Hameed, S. Thomas, O.S. Oluwafemi, N. Kalarikkal, Investigating physico-chemical properties, excited state properties, virtual bioactivity
solvent effects on aggregation behavior, linear and nonlinear optical properties screening and SERS analysis of three guanine based antiviral drugs,
of silver nanoclusters, Opt. Mater. 73 (2017) 695–705, https://doi.org/10.1016/ valacyclovir HCl hydrate, acyclovir and ganciclovir, Polycyclic Aromat.
j.optmat.2017.09.024. Compd. (2020), https://doi.org/10.1080/10406638.2020.1773876.
[22] Yong Jiang, Yuanyuan Huang, Hao Cheng, Qinghua Liu, Zhi Xie, Tao Yao, Zheng [44] Noel M. O’boyle, Adam L. Tenderholt, Karol M. Langner, Cclib: a library for
Jiang, Yuying Huang, Qing Bian, Guoqiang Pan, Zhihu Sun, Shiqiang Wei, package independent computational chemistry algorithms, J. Comput. Chem.
Solvent influence on the role of thiols in growth of thiols-capped Au 29 (5) (2008) 839–845, https://doi.org/10.1002/jcc.20823.
nanocrystals, J. Phys. Chem. C 118 (1) (2014) 714–719, https://doi.org/ [45] V. Barone, M. Cossi, Quantum calculation of molecular energies and energy
10.1021/jp408926n. gradients in solution by a conductor solvent mode, J. Phys. Chem. A 102 (1998)
[23] Meng Zhou, Saran Long, Xiankai Wan, Yang Li, Yingli Niu, Qianjin Guo, Quan- 1995–2001, https://doi.org/10.1021/jp9716997.
Ming Wang, Andong Xia, Ultrafast relaxation dynamics of phosphine- [46] A.M. Teale, F. De Proft, D.J. Tozer, Orbital energies and negative electron
protected, rod-shaped Au20 clusters: interplay between solvation and affinities from density functional theory: Insight from integer discontinuity, J.
surface trapping, Phys. Chem. Chem. Phys. 16 (34) (2014) 18288–18293, Chem. Phys. 129 (2008), https://doi.org/10.1063/1.2961035 044110.
https://doi.org/10.1039/C4CP02336F. [47] Kieron Burke, Lucas O. Wagner, DFT in a nutshell, Int. J. Quantum Chem. 113
[24] Baoqi Yin, Zhixun Luo, Coinage metal clusters: from superatom chemistry to (2) (2013) 96–101, https://doi.org/10.1002/qua.24259.
genetic materials, Coord. Chem. Rev. 429 (2021) 213643, https://doi.org/ [48] Ralph G. Pearson, Absolute electronegativity and hardness: Application to
10.1016/j.ccr.2020.213643. inorganic chemistry, Inorg. Chem. 27 (4) (1988) 734–740, https://doi.org/
[25] Manohar Pillegowda, Ganga Periyasamy, DFT studies on the influence of 10.1021/ic00277a030.
ligation on optical and redox properties of bimetallic [Au4M2] clusters, RSC [49] Huifang Xu, David C. Xu, Yifeng Wang, Natural indices for the chemical
Adv. 6 (89) (2016) 86051–86060, https://doi.org/10.1039/C6RA14886G. hardness/softness of metal cations and ligands, ACS Omega 2 (10) (2017)
[26] Alfredo Tlahuice-Flores, Ligand effects on the optical and chiroptical properties 7185–7193, https://doi.org/10.1021/acsomega.7b0103910.1021/
of the thiolated Au18 cluster, Phys. Chem. Chem. Phys. 18 (40) (2016) 27738– acsomega.7b01039.s001.
27744, https://doi.org/10.1039/C6CP04298H. [50] R.K. Roy, S. Krishnamurti, P. Geerlings, S. Pal, Local softness and hardness based
[27] D.M. Govindachar, G. Periyasamy, DFT studies on ureido-peptide functinalized reactivity descriptors for predicting intra- and intermolecular reactivity
Au4M2 bimetallic nanoclusters, Chem. Phys. Lett. 753 (2020), https://doi.org/ sequences: Carbonyl compounds, J. Phys. Chem. A 102 (1998) 3746-3755.
10.1016/j.cplett.2020.137612 137612. https://doi.org/10.1021/jp973450v
[28] Laura Fabris, Sabrina Antonello, Lidia Armelao, Robert L. Donkers, Federico [51] A. Nicolai, B.G. Sumpter, V. Meunier, Tunable water desalination across
Polo, Claudio Toniolo, Flavio Maran, Gold nanoclusters protected by graphene oxide framework membranes, Phys. Chem. Chem. Phys. 16 (2014)
conformationally constrained peptides, J. Am. Chem. Soc. 128 (1) (2006) 8646–8654, https://doi.org/10.1039/C4CP01051E.
326–336, https://doi.org/10.1021/ja056058110.1021/ja0560581.s001. [52] S. Li, Semiconductor Physical Electronics, second ed., Springer, Berlin, 2006.
[29] Q. Yuan, Y. Wang, L. Zhao, R. Liu, F. Gao, L. Gao, X. Gao, Peptide protected gold [53] P. Selvarengan, P. Kolandaivel, Studies of solvent effects on conformers of
clusters: chemical synthesis and biomedical applications, Nanoscale 8 (2016) glycine molecule, J. Mol. Struct. Theochem. 617 (1-3) (2002) 99–106, https://
12095–12104, https://doi.org/10.1039/C6CR02750D. doi.org/10.1016/S0166-1280(02)00421-9.
[30] Hui Wang, Xu Li, Liang Gao, Jiao Zhai, Ru Liu, Xueyun Gao, Dongqi Wang, Lina [54] A.J.A. Aquino, D. Tunega, G. Haberhauer, M.H. Gerzabek, H. Lischka, Solvent
Zhao, Atomic structure of a peptide coated gold nanocluster identified using effects on hydrogen bonds - a theoretical study, J. Phys. Chem. A 106 (2002)
theoretical and experimental studies, Nanoscale 8 (22) (2016) 11454–11460, 1862-1871. https://doi.org/10.1021/jp013677x
https://doi.org/10.1039/C5NR08727A. [55] Jacopo Tomasi, Benedetta Mennucci, Roberto Cammi, Quantum mechanical
[31] Ofer I. Wilner, Itamar Willner, Functionalized DNA nanostructures, Chem. Rev. continuum solvation models, Chem. Rev. 105 (8) (2005) 2999–3094, https://
112 (4) (2012) 2528–2556, https://doi.org/10.1021/cr200104q. doi.org/10.1021/cr9904009.
[32] T.L. Silbaugh, P. Devlaminck, J.A. Sofranko, M.A. Barteau, Selective oxidation of [56] R. Ghiasi, A quantum chemical investigation of the influence of solvent
ethanol over Ag, Cu and Au nanoparticles supported on Li2O/c-Al2O3, J. Catal. polarity on the structural, electronic, spectroscopic properties and
364 (2018) 40–47, https://doi.org/10.1016/j.cat.2018.05.011. hyperpolarizability in molybdenum silylidyne complex CpMo(CO)2(Si-Ph),
[33] R.-Y. Wang, J.-X. Wang, J. Jia, H.-S. Wu, The growth pattern and electronic J. Mol. Liq. 264 (2018) 616–620, https://doi.org/10.1016/j.molliq.2018.05.068.
structures of Cun(n=1-14) clusters on rutile TiO2(1 1 0) surface, Applied Surface [57] M. Rahimi, R. Ghiasi, Solvent effect on isomerization reaction of [(g5 –C5H5)
Science 536 (2021) 147793. https://doi.org/10.1016/j.apsusc.2020.147793 (CO)2Re=C(C2HB10) (C6H5)] carbene complex to [(g5 – C5H5)(CO)

9
J.S. Al-Otaibi, Y. Sheena Mary, Y. Shyma Mary et al. Journal of Molecular Liquids 345 (2022) 118242

(COC2HB10H10)ReCC6H5]carbine complex: a computational investigation, J. [63] Bhaskaran Sureshkumar, Yohannan Sheena Mary, Chacko Yohannan Panicker,
Mol. Liq. 265 (2018) 164–171, https://doi.org/10.1016/j.molliq.2018.04.154. Somasekharan Suma, Stevan Armaković, Sanja J. Armaković, Christian Van
[58] M. Kiani, R. Ghiasi, H. Pasdar, B. Mirza, Computational investigation of solvent Alsenoy, Badiadka Narayana, Quinoline derivatives as possible lead
polarity effect on the structure and properties of (OC)4Cr-biscarbene complex compounds for anti-malarial drugs: Spectroscopic, DFT and MD study,
in the singlet ground state and lowest singlet excited state, J. Mol. Liq. 300 Arabian J. Chem. 13 (1) (2020) 632–648.
(2020), https://doi.org/10.1016/j.molliq.2019.112327 112327. [64] Y.S. Mary, H.T. Varghese, C.Y. Panicker, M. Girisha, B.K. Sagar, H.S. Yathirajan, A.
[59] Mahendiraprabu Ganesan, Nirmala Vedamanickam, Selvarengan A. Al-Saadi, C. Van Alsenoy, Vibrational spectra, HOMO, LUMO, NBO, MEP
Paranthaman, Studies of intramolecular H-bond interactions and solvent analysis and molecular docking study of 2,2-diphenyl-4-(piperidin-1-yl)
effects in the conformers of glycolic acid-a quantum chemical study, J. Theor. butanamide, Spectrochim. Acta 150 (2015) 543–556. https://doi.org/
Comput. Chem. 17 (01) (2018) 1850009, https://doi.org/10.1142/ 10.1016/j.saa.2015.05.090
S0219633618500098. [65] Jamelah S. Al-Otaibi, Detailed quantum mechanical studies on bioactive
[60] Parisa Parsa, Reza Ghiasi, Azam Marjani, Unveiling the influence of solvent benzodiazepine derivatives and their adsorption over graphene sheets,
polarity on structural, electronic properties, and 31P NMR parameters of Spectrochim. Acta 235 235 (2020) 118333, https://doi.org/10.1016/j.
rhenabenzyne complex, Inrog. Chem. Commun. 127 (2021) 108497, https:// saa.2020.118333.
doi.org/10.1016/j.inoche.2021.108497. [66] Jamelah S. Al-Otaibi, Aljawhara H. Almuqrin, Y. Sheena Mary, Y. Shyma Mary,
[61] Renyer A. Costa, Jonathas N. da Silva, Viviane G. Oliveira, Lucas M. Anselmo, Comprehensive quantum mechanical studies on three bioactive anastrozole
Míriam M. Araújo, Kelson M.T. Oliveira, Rita de Cássia S. Nunomura, New based triazole analogues and their SERS active graphene complex, J. Mol.
insights into structural, electronic, reactivity, spectroscopic and Struct. 1217 (2020) 128388, https://doi.org/10.1016/j.molstruc.2020.128388.
pharmacological properties of bergenin: experimental, DFT calculations, MD [67] U. Bhattacharyya, T. Pooventhiran, R. Thomas, Adsorption of the drug bempedoic
and docking simulations, J. Mol. Liquid. 330 (2021) 115625, https://doi.org/ acid over different 2D/3D nanosurfaces and enhancement of Raman activity
10.1016/j.molliq.2021.115625. enabling ulstrasensitive detection: First principle analysis, Spectrochim. Acta
[62] Y.S. Mary, C.Y. Panicker, M. Sapnakumari, B. Narayana, B.K. Sarojini, A.A. Al- 254 (2021), https://doi.org/10.1016/j.saa.2021.119630 119630.
Saadi, C. Van Alsenoy, J.A. War, H.K. Fun, Molecular structure, FT-IR, [68] R.F.W. Bader, Atoms in molecules, Acc. Chem. Res. 18 (1985) (1985) 9–15,
Vibrational assignments, HOMO-LUMO analysis and molecular docking https://doi.org/10.1021/ar00109a003.
study of 1-[5-(4-Bromophenyl)-3-(4-fluorophenyl)-4,5-dihydro-1H-pyrazol- [69] Hossein Roohi, Ali-Reza Nowroozi, Elham Anjomshoa, H-bonded complexes of
1-yl]ethanone, Spectrochim. Acta 136 (2015) 473–482, https://doi.org/ uracil with parent nitrosamine: a quantum chemical study, Comput. Theor.
10.1016/j.saa.2014.09.060. Chem. 965 (1) (2011) 211–220, https://doi.org/10.1016/j.comptc.2011.01.048.

10