J Incl Phenom Macrocycl Chem

DOI 10.1007/s10847-017-0711-y

ORIGINAL ARTICLE

Structure, electronic, inclusion complex formation behavior

and spectral properties of pillarplex
Natarajan Sathiyamoorthy Venkataramanan1,2 · Ambigapathy Suvitha1

Received: 15 February 2017 / Accepted: 28 March 2017

© Springer Science+Business Media Dordrecht 2017

Abstract Electronic structure, vibrational and NMR
spectra of metal-Pillarplex (metal = Cu, Ag and Au) and
its inclusion complex with 1,8-diaminooctane (DAO) are
investigated by using density functional theory. The coor-
dinated metal atoms tune the cavity size and the height of
metal-Pillarplex and form a rigid cavity thereby reducing
their structural deformation. Cu-Pillarplex undergoes a
large deformation both on the host and guest molecule. The
calculated Gibbs free energy for the formation of inclu-
sion complex were negative indicating their facile forma-
tion at the room temperature. Computed binding energies
with various functionals and energy decomposition analy-
sis, shows that dispersion correction is essential in these
systems. The low binding energy, and the physical adsorp-
tion of guest molecule and HOMO–LUMO spatial dia-
gram indicates, that the Au and Ag-Pillarplex can be used
as reversible host for linear alkanes Complexation of guest
engenders frequency shift in the vibrational spectra. Calcu-
lated 1H NMR reveal that guest protons which are closer to
the metal sites experience larger shielding possibly due to
C–H→LP* metal interaction. The 15N signal observed for
the DAO is nearly identical to that observed for the DAO@
metal-Pillarplex. NBO and AIM analysis indicate that
metal centers in host, play a major role in stabilizing the
guest inside the cavity than the amino group on the guest
molecule.

Electronic supplementary material The online version of this

article (doi:10.1007/s10847-017-0711-y) contains supplementary
material, which is available to authorized users.

* Natarajan Sathiyamoorthy Venkataramanan

nsvenkataramanan@gmail.com; venkataramanan@scbt.
sastra.edu
1
Department of Chemistry, School of Chemical
and Biotechnology, SASTRA University, Thanjavur 613401,
India
2
Center for Computational Chemistry and Materials Science
(CCCMS), SASTRA University, Thanjavur 613401, India

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Graphical Abstract
Keywords Pillarplex · DFT · NBO · AIM · NMR
Introduction
In the past few decades, supramolecular chemistry based
on molecular recognition and self-assembly of synthetic
macrocycles has been under intensive investigation, due to
their interesting topological structures and excellent tun-
able host–guest properties [1–3]. The nature and use of the
macrocycles are decided by their shape, synthesis, solubil-
ity in organic solvents and aqueous media, their functional-
ization and their host–guest binding ability [4]. Among the
macrocyclic molecules, the selective molecular recognition
and self-assembly properties of several classical supramo-
lecular macrocycles, including that of, crown ethers [5],
cyclophanes [6], cyclodextrins (CDs) [7, 8], cucurbit[n]
urils (CB[n]) [9, 10], calix[n]arenes [11, 12], and Pillar[n]
arenes [13] were well documented. Furthermore, most of
these macrocycles are neutral molecules and are capable of
binding charged guest molecules.
On the contrary, organometallic complexes have hardly
been used as macrocycles, as their required cavitand
structures are not trivially feasible via classical coordina-
tion chemistry [14]. Furthermore, the presence of transi-
tion metals may create paramagnetic centers on them. In
13
J Incl Phenom Macrocycl Chem
addition, the synthesis of such supramolecular complexes
are unpredictable and can lead to the formation of multi-
metallic clusters. Additionally, the formed supramolecules
can also be air and moisture sensitive, thereby limiting their
application [15]. Recently, there have been several reports
on metallo-cavitands, rectangles, cages and nano-cap-
sules, which are found to be either fluorogenic sensors for
metal ions or capable of selective binding of heavy metals
[16–19].
Among the organometallic host-systems, the one with
coinage metals have crucial advantages such as potential
intrinsic photoluminescent properties, straightforward syn-
theses, and the possibility of post-synthetic modifications
while exhibiting a high stability against air and moisture
[20]. Very recently, Altmann and Pöthig, synthesized a
new metal–organic supramolecular host which resemble
the organic pillar[n]arenes and are named as pillarplex.
These pillarplex do have Group 11 elements silver or gold
as metal centers [21]. The pillarplex ­(M8(LMe)2)4+ (M = Ag,
Au) has the integrated advantages of facile preparation,
symmetrical and pillar shaped architecture, high rigidity,
emissive in the blue region and with high cationic charge.
To understand the molecular recognition ability of the
pillarplex, Altmann and Pöthig used 1,8-diaminooctane
(DAO) as guest molecule and complexation was followed
by nuclear magnetic resonance (NMR) spectroscopy. Job-
plot analysis showed the formation of 1:1 stoichiometry,
J Incl Phenom Macrocycl Chem
which was further supported by the single crystal analy-
sis of supramolecular complexes between the Au-Pillar-
plex and DAO molecule. The calculated binding con-
stant was found to be K ­ d = 24.0 ± 5.4 µM, close to the
values observed for the cucurbituril systems, which are
considered to have a binding energy almost equivalent
to that of biological biotin-avidin pair [22]. Attempt to
use 1,1′-dioctadecyl viologen bromide and p-phenylen-
ediamine, as guest molecules, does not show any high
field shift of the aromatic protons, indicating no binding
between the guest and the host molecules. Thus, a size-
exclusion was shown by the metallocavitand when mol-
ecules other than linear structures were used.
In spite of the above experimental investigation, there
exists a need for theoretical investigation on the elec-
tronic properties and inclusion formation capabilities of
the metal-Pillarplex. It should be pointed out here pillar-
plex with metal Ag and Au were synthesized while the
same group 11 element Cu has not been synthesized. In
the present work, we endeavor to explain the complex
formation capabilities of pillarplex (metals = Cu, Ag
and Au) with DAO molecule in different orientation by
using various density functional methods including the
dispersion corrected density functional theory (DFT-
D) method. The scheme depicting the molecules stud-
ied are shown in Scheme 1. By using quantum theory of
atoms-in-molecules (QTAIM), natural bond order (NBO)
analysis, and the energy decomposition analysis (EDA)
we have analyzed the nature of interaction between the
metal-Pillarplex and DAO molecule. Spectral studies
using 1H, 13C NMR, and vibration analysis were carried
out to understand the nature of interaction. This study
will help to understand the mechanism of selective com-
plexation of linear molecules by pillarplex at molecular
level, which would be useful for their future exploitation
and their applications.
Scheme 1  Schematic representation and numbering scheme for metal-Pillarplex and DAO molecule
Computational details
All the DFT calculations were performed using the Gauss-
ian 09 program package [23]. The structural optimization
was carried without any symmetry constraints using the
BP86 functional, with the Grimme’s D2 correction [24].
In order to speed up the calculation, we used the density
fitting procedure used for the pure functionals. According
to previous studies BP86-D2 functional provide reasonably
accurate interaction energies in large noncovalent com-
plexes [25]. The initial geometry of the Au-Pillarplex was
taken from the crystal structure reported earlier [21]. We
have used the Stuttgart–Dresden ECPs designated as SDD
for geometrical optimization and to compute the vibra-
tional frequencies. Harmonic vibrational frequencies are
computed using BP96-D2/SDD method on the minimum
energy geometries to verify them to be at the minimum
on the potential surface. To verify quality of BP96-D2/
SDD method in geometrical optimization the coordinates
of the crystal structure with the DAO cavity inside the Au-
Pillarplex is superimposed with the coordinates obtained in
the DFT calculation (See supporting information Fig. S1).
From the Fig. S1, it is evident that the geometrical param-
eters are well reproduced by the BP86-D2/SDD level of
theory. Furthermore, the choice of BP86-D2/SDD method
for geometrical optimization is justified as a compromise
between reliable results and reasonable computational cost.
The binding energy of the guest molecules is computed
using the supramolecular approach [26].
Partial charge analysis was done using the NBO pro-
gram as implemented in Gaussian 09 program at the BP96-
D2/SDD//B3LYP-D3/SDD level of theory [27]. In order to
gain further insights into the nature of bonding that exists,
topological analysis has been performed using AIMALL
package, and the corresponding wave functions were gen-
erated at the B3LYP-D3/SDD level of theory. The details
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 J Incl Phenom Macrocycl Chem

on the AIM analysis can be found in our previous paper
[28]. The energy decomposition analysis (EDA) is carried
out at the BP86-D3/SDD//B3LYP-D3/TZ2P level using
Amsterdam density functional program package. In EDA,
the total binding energy (ΔEbind) is decomposed into four
terms, viz., Pauli repulsion (ΔEPauli), electrostatic (ΔEelstat),
orbital (ΔEorb), and dispersion (ΔEdisp) terms [29]. For
performing EDA analysis, the DAO guest molecule is con-
sidered as one fragment and the metal-Pillarplexes as the
other fragment. The repulsive term ΔEPauli accounts for the
repulsive Pauli interaction between the occupied orbitals
of two interacting fragments. The attractive terms ΔEelstat
and ΔEorb represent the classical electrostatic interactions
between two fragments and the interactions between occu-
pied molecular orbitals of one fragment with the unoccu-
pied molecular orbitals of another fragment, called charge
transfer, as well as polarization and electron pair bonding,
respectively. The term ΔEdisp represents the dispersion
interaction between two interacting fragments.
The effect of acetonitrile as solvent, was implemented
using the CPCM method, with sphere radii optimized for
COSMO-RS proposed by Klamt [30]. NMR chemical shifts
(δ) were computed in acetonitrile medium at the B3LYP/
SDD level of theory. The reported 1H and 13C chemical
shifts were obtained by subtracting the nuclear magnetic
shielding tensors of proton in pillarplex and DAO molecule
from those in the tetramethylsilane (as reference) using the
gauge-independent atomic orbital (GIAO) method.
Our previous studies on inclusion complexes provided
us a clue that the guest molecules prefer to get encapsu-
lated inside the cavity, rather than on a surface adsorption
[31, 32]. Furthermore, the reported X-ray crystal struc-
ture for the Au-Pillarplex has the DAO molecule inside
the cavity [22]. Thus, in the present study, we have con-
sidered only the encapsulated system. The superimposed
geometries obtained at the gas phase along with the
reported X-ray structure of DAO@Au-Pillarplex is pro-
vided in supporting information Fig. S1. From the Fig.
S1, it is evident that the geometrical parameters are well
reproduced by the BP86-D2/SDD level of theory. The
optimized structure of the free DAO molecules is found
to have different geometries out of which, the all anti con-
formation was found to have the lowest energy. The other
higher energy geometries in which all the C ­ H2 groups
exists with anti-conformations are shown in supporting
information Fig. S2, in which the amino groups in slight
twisted from the lowest energy conformer. The optimized
structures of the inclusion complexes are depicted in
Fig. 1. It is evident form the Fig. 1, that in the case of

Results and discussions

Geometry and binding ability of hosts

The initial geometry of the pillarplex is taken form

the X-ray crystal structure reported for the Au-
pillarplexes@1,8-diaminooctane molecule [22]. The guest
molecule was removed and was optimized without any
geometrical constrains at BP86-D2/SDD level of theory.
The height and cavity size of the pillarplex depends on the
coordinated metal atom. When Ag is the metal, the height
measured between the hydrogen atoms of opposite imida-
zole rings was 11.58 Å, while Au and Cu have 10.32 and
10.05 Å height respectively. The width near the metal cent-
ers also vary depending on the metal. On the Au-Pillarplex,
the width measured was 8.06 Å, while in Ag-Pillarplex
and Cu-Pillarplex the measured width was 7.93 and 7.94 Å
respectively. The width at the penetrable cavity was highest
for the Ag-Pillarplex with 9.25 Å and lowest for the Cu-Pil-
larplex with 8.97 Å. The computed width at the penetrable
cavity for the Au-Pillarplex was close to the Ag-Pillarplex.
Thus, the coordinated metal atoms tune the cavity size and Fig. 1  Top (perspective) and side views of optimized geometries of
the height of metal-Pillarplex. DAO@metal-Pillarplex with metals Cu, Ag, and Au

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J Incl Phenom Macrocycl Chem
Ag and Au metal-Pillarplex the DAO molecule is fully
encapsulated inside the cavity, while with Cu-Pillarplex,
the molecule is partially expelled out of the cavity and
one of the nitrogen atom get bonded with the Cu atom.
In the metal-Pillarplex, for the full inclusion of DAO
molecule inside the cavity, the guest or host need to
undergo a deformation in structure. Notice that DAO mol-
ecule has 12.17 Å length, while the metal-Pillarplex have
10.05–11.58 Å length. If the metal-Pillarplex are consid-
ered to be rigid then, one could anticipate that larger defor-
mation to occur on the guest molecules. To confirm the
above discussion, we calculated the deformation energies
for the above inclusion complexes. The computed defor-
mation energies on the host and the DAO molecule both
in the gas phase and in solvent are provided in Table 1. It
is found that Cu-Pillarplex undergoes a large deformation
both on the host and DAO molecule. It should be pointed
out that the DAO molecule is only partially inserted inside
the cavity in the case of Cu-Pillarplex. Furthermore, one
of the amino group is bonded to the Cu metal. Thus, it is
not surprising to see a larger deformation on the host and
guest molecule in the Cu-Pillarplex. On the contrary, for
the Ag and Au-Pillarplex, a very minimal structural defor-
mation is observed both on the host and DAO molecule.
On the guest molecules, deformation energies were 1.07
and 1.36 kcal mol−1 for the Ag and Au-Pillarplex respec-
tively. In order to understand the inclusion of nonlinear
molecules inside the cavity of the pillarplex, we introduced
the 4-methylpeptane-1,7-diamine. Upon optimization, we
observed large deformation in the structure of Au-Pillar-
plex indicating that, linear molecules could be more stabi-
lized inside the cavity of pillarplex. Furthermore, structural
deformation has not been observed in the solution phase
when the linear molecule DAO was used, which indicates
the structural rigidity of the guest molecule.
Binding ability of hosts
We then computed the binding energy of the DAO mol-
ecules to the host metal-Pillarplex, at the BP86-D2/SDD//
Table 1  Total binding energies ­(Ebind in kcal/mol) for the inclusion
complexes computed at BP86-D2/SDD//B3LYP-D3/SDD level in gas
and solution phase, strain energies on the host pillarplex’s and guest
Metal Ebind (kcal mol−1)
Gas Acetonitrile
Cu −53.25 −42.34
Ag −53.06 −49.40
Au −56.04 −52.23
a
Computed at BP86/SDD//B3LYP-D3/SDD level
b
Values in parenthesis are in solution phase
B3LYP-D3/SDD level of theory. The binding energy is
computed as the energy difference between the total energy
of the inclusion complex and the energy obtained for the
individual components namely the metal-Pillarplex and
DAO molecule. The computed binding energies are found
to be almost identical for all the metal-Pillarplex in the gas
phase. While, in the solution phase we observe that Au-
Pillarplex to have the highest binding energy. Furthermore,
we observe a decrease in the binding energy by an order of
10 kcal mol−1 for the Ag and Cu-Pillarplex. To investigate
the thermodynamic parameter for the formation of inclu-
sion complex we computed the Gibbs free energy using
the statistical thermodynamic calculations at 1 atm pres-
sure and 298 K. The computed Gibbs free energy for all the
complexes were negative indicating that the formation of
inclusion complex would be facile at the room temperature.
However, the computed Gibbs free energy is lowest for the
Cu-Pillarplex, whereas, Ag and Au-Pillarplex have almost
the same formation energy. The lowest Gibb’s free energy
of formation for Cu-Pillarplex can be attributed to the com-
plexation of ligand to the Cu metal centers.
In order to access the performance of various function-
als, the binding energies are computed using the follow-
ing functionals, BLYP, BP86, PBEPBE (GGA functional),
B3LYP, PBE0 (hybrid-GGA functional), and B3LYP-D3,
PBE0-D3 (range separated hybrid-GGA functional with
dispersion correction). The computed interaction energies
for the inclusion complexes are obtained on the optimized
geometry at the BP86-D2/SDD level of theory and the
energies are computed using the various functionals which
are provided in the Table 2. It is interesting to observe that
the computed binding energies are largely unfavorable for
the popular hybrid functional B3LYP and pure functional
BLYP. The use of hybrid functional along with the disper-
sion correction has improved the binding energy of these
system. In dispersion functional, the attractive part of the
van der Waals type interaction potential between atoms and
molecules that are not directly bounded to each other are
empirically well defined. Hence, the DFT-D methods can
provide better accuracy with less computational cost [33].
DAO (in kcal/mol) HOMO–LUMO energy gap ­(Egap in eV) and free
energy of formation (ΔG in kcal/mol) for the formation of inclusion
complexes computed at the BP86-D2/SDD// B3LYP-D3/SDD level
Strain Energy (kcal mol−1)a Egap (eV) ΔG
Pillarplex Guest
11.36 (11.21)b 4.72 (4.97) 2.32 (2.97) −26.05
0.11 (0.47) 1.07 (1.03) 2.94 (3.13) −33.70
0.40 (0.74) 1.36 (1.01) 2.65 (3.13) −33.44
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 J Incl Phenom Macrocycl Chem

Table 2  Total binding energies ­(Ebind in kcal/mol) for the inclusion complexes computed on the BP86-D2/TZVP optimized geometry using
various functionals
MP M = Ebind (kcal mol−1)
BP86 BLYP PBEPBE B3LYP PBE1PBE BP86-D2 BP86-D3 B3LYP-D3 B3LYP-D3BJ PBE1PBE-D3

Cu −0.57 3.43 −10.06 1.54 −6.76 −43.47 −49.84 −42.34 −39.66 −38.00
Ag 5.65 6.73 −7.26 3.13 −5.22 −49.92 −54.50 −49.40 −49.17 −42.88
Au −5.09 6.39 −7.57 2.92 −5.47 −65.06 −57.65 −52.23 −50.43 −44.90

Furthermore, the use of Becke–John damping reduces the
binding energy. These results show that proper functionals
with dispersion correction has to be used in calculating the
binding energy in these systems.
To understand the kinetic stability of these inclu-
sion complexes, we computed the energy separation of
the highest occupied molecular orbital (HOMO) and
the lowest unoccupied molecular orbital (LUMO). The
HOMO–LUMO gaps (Egap) computed for the inclusion
complexes are provided in Table 1. The metal-Pillarplex
have an Egap 2.32–2.94 eV, while the inclusion complexes
have lower values. The Egap for the guest molecule was
6.37 eV, which indicates that the guest molecule is chemi-
cally stable compared to the host molecule. The lower Egap
for the inclusion complex shows that complex formation
can be a reversible process and are kinetically controllable.
The frontier orbital for Ag-Pillarplex and its inclusion com-
plex at the DFT-D3 level are provided in Fig. 2. The spatial
orbital diagram for Au-Pillarplex and Cu-Pillarplex and its
inclusion complexes are provided in supporting information
Figs. S3–S4. From the Fig. 2 and Figs. S3–S4, it is evident
that the HOMO and LUMO energies are located mainly on
the host molecule, indicating that the encapsulated ligand
does not alter the electronic structure of the Ag and Au-
Pillarplex and the encapsulation occurs by a pure physical
adsorption process [34]. On the contrary, in the Cu-Pillar-
plex, we observe a different trend, in which the DAO has a
partial orbital contribution both at HOMO and LUMO level
which may be attributed to the metal-complex formation of
the DAO with Cu metal. The low binding energy, and the
physical adsorption of DAO and HOMO–LUMO spatial
diagram indicates, that the Au and Ag-Pillarplex’s can be
used as reversible host for linear alkanes. Since, our main
aim to study the inclusion complexes with noncovalent
interactions, in our further discussion we have excluded the
Cu-Pillarplex.
NBO analysis
The net charges on the pristine ligand and after complex
formation were computed using the NBO method and are
provided in supporting information Table S1. From the

Fig. 2  Top (perspective) and side views of HOMO and LUMO orbital spatial diagram for the Ag-Pillarplex and DAO@Ag-Pillarplex complex

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J Incl Phenom Macrocycl Chem

Table S1, it is evident that the net charges on the nitrogen
atom increases, while the change on the alkane hydrogen
atom decreases. Furthermore, there has been an increase in
charge on the amine hydrogen atoms. On the contrary, the
charge on the metal atoms in the host molecule has not sig-
nificantly changed. This behavior can be explained by the
change transfer from the cationic host metal-Pillarplex to
the ligand.
To estimate more precisely the character of the
host–guest interactions, NBO analysis is carried out at the
B3LYP-D3/SDD level of theory in acetonitrile solvent on
the optimized geometry. More details about NBO can be
found in the previous report [35]. Since the host metal-Pil-
larplex has a significant charge on it, we have considered
DAO as donor NBO and metal-Pillarplex as acceptor NBO.
The E(2) values corresponding to the orbital interactions
from the ligand to metal-Pillarplex with a threshold higher
than 0.75 kcal mol−1 are listed in Table 3. It is interesting to
observe that most of the interaction arises due to the metal
center. The larger the E(2) value, the more intensive is the
intramolecular interaction between the metal-Pillarplex
and DAO. The strongest intramolecular interaction in Ag-
Pillarplex is the electron donation from methylene hydro-
gen to the antibonding lone pair orbital of silver metal.
The corresponding interaction for the Au-Pillarplex has a
E(2) of 1.19 kcal mol−1. In addition to the antibonding lone
pair orbital involvement in the bonding we also observe the
involvement of antibonding Rydenberg orbital in Au-Pillar-
plex. This may due to the larger size of the Au atom com-
pared to the Ag atom center in the host. Furthermore, the
E(2) values are very similar in both the metal-Pillarplex and
hence it is not surprising to have a similar binding energy
in these inclusion complexes.
Electron density and energy decomposition analysis
The electron density (ρ), and its Laplacian (∇2ρ), the poten-
tial energy density (V(r)), Kinetic energy density (G(r)),
total energy denisty (H(r)), and bond ellipticity, (εb), for the
intramolecular bond critical point (BCP) were obtained by
the AIM method and are provided in Table 3 for Ag-Pillar-
plex and in Table 4 for Au-Pillarplex. The molecular graph
for DAO@metal-Pillarplex obtained is provided in Fig. 3.
The number of intramolecular BCP differ between the
Ag-Pillarplex and Au-Pillarplex. In the Ag-Pillarplex, we
observed 38 BCP’s, while Au-pillarplex has 30 BCP’s. The
observed ring critical points (RCP) and cage critical points
(CCP) were found to be 54 and 23 in Ag-pillarplex, while
Au-pillarplex has 52 and 23 RCP’s and CCP’s respectively.
The quantity of electron density at the BCP provides
the information about the nature and strength of bond-
ing between the two monomers in any inclusion complex

Table 3  Selected Metal = Ag Metal = Au

intramolecular acceptor–donor
interactions and second order Donor (i) Acceptor (j) E(2) Donor (i) Acceptor (j) E(2)
perturbation energies (in kcal/
mol) for between metal- σ (1) H14–C5 LP*(7)Ag6 1.21 σ (1) H14–C5 LP*(8)Au6 1.19
Pillarplex and DAO in DAO@ σ (1) H13–C5 LP*(7)Ag7 1.18 σ (1) H14–C5 LP*(8)Au7 1.01
metal-Pillarplex complexes σ (1) H12–C4 LP*(8)Ag1 1.01 σ (1) H9–C3 RY*(20)Au3 1.04
σ (1) H11–C4 LP*(8)Ag4 1.01 σ (1) H9–C3 LP*(8)Au1 0.98
σ (1) H14–C5 LP*(7)Ag7 0.97 σ (1) H9–C3 LP*(8)Au3 0.82
σ (1) H13–C5 LP*(7)Ag6 0.96 σ (1) H9–C3 RY*(13)Au3 0.78
σ (1) H9–C3 LP*(8)Ag4 0.95 σ (1) H9–C3 RY*(7)Au4 0.75
σ (1) H12–C4 LP*(8)Ag2 0.92 σ (1) H10–C3 LP*(8)Au1 0.92
σ (1) H11–C4 LP*(7)Ag8 0.92 σ (1) H10–C3 LP*(8)Au2 0.84
σ (1) H11–C4 LP*(8)Ag3 0.91 σ (1) H10–C3 RY*(20)Au2 0.81
σ (1) H12–C4 LP*(7)Ag5 0.88 σ (1) H11–C4 LP*(8)Au3 1.19
σ (1) H10–C3 LP*(8)Ag1 0.85 σ (1) H11–C4 LP*(8)Au 4 1.16
σ (1) H12–C4 LP*(8)Ag4 0.79 σ (1) H11–C4 RY*(z1)Au8 0.8
σ (1) H9–C3 LP*(8)Ag3 0.79 σ (1) H11–C4 RY*(13)Au8 0.75
σ (1) H9–C3 σ *(1)C21–Ag3 0.77 σ (1) H12–C4 LP*(8)Au2 1.32
σ (1) H10–C3 LP*(8)Ag2 0.76 σ (1) H12–C4 LP*(8)Au1 1.16
– – – σ (1) H12–C4 σ*(1)C73–Au1 0.82
– – – σ (1) H13–C5 LP*(8)Au7 1.11
– – – σ (1) H13–C5 LP*(8)Au6 1.05
– – – σ (1) H13–C5 LP*(8)Au4 0.84
– – – σ (1) H13–C5 LP*(8)Au3 0.82

*For atom numbering see Scheme 1

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 J Incl Phenom Macrocycl Chem

Table 4  Topological BCP ρ −∇2ρ V(r) G(r) H(r) εb

parameters obtained from
AIM analysis for the DAO@ H13–Ag7 0.00763 0.02404 −0.00388 0.00494 0.00107 0.09626
Ag-Pillarplex
H14–Ag6 0.00870 0.02724 −0.00469 0.00575 0.00106 0.06414
H14–Ag2 0.00367 0.01084 −0.00143 0.00207 0.00064 1.25672
H12–Ag1 0.00772 0.02364 −0.00394 0.00492 0.00099 0.04710
H12–Ag5 0.00453 0.01399 −0.00190 0.00270 0.00080 0.34433
H11–Ag8 0.00513 0.01596 −0.00224 0.00311 0.00088 0.44882
H11–Ag4 0.00699 0.02152 −0.00343 0.00440 0.00098 0.07181
H9–Ag3 0.00649 0.01939 −0.00291 0.00388 0.00097 0.29990
H10–Ag2 0.00508 0.01483 −0.00206 0.00288 0.00082 0.38454
H16–Ag8 0.00581 0.01720 −0.00238 0.00334 0.00096 1.02717
H15–Ag5 0.00484 0.01431 −0.00182 0.00270 0.00088 2.18744
N*–H15 0.00323 0.01058 −0.00127 0.00196 0.00069 0.74963
N*–H13 0.00428 0.01357 −0.00169 0.00254 0.00085 1.45474
H10–Ag2 0.00508 0.01483 −0.00206 0.00288 0.00082 0.38454
H8–Ag3 0.00649 0.01939 −0.00291 0.00388 0.00097 0.29990
N*–H9 0.00366 0.01264 −0.00151 0.00233 0.00083 0.27326
H10–N* 0.00413 0.01443 −0.00172 0.00266 0.00094 0.28853
C*–H8 0.00430 0.01434 −0.00173 0.00266 0.00093 0.53753
C*–H8 0.00276 0.00888 −0.00094 0.00158 0.00064 1.18349
C*–H7 0.00249 0.00778 −0.00083 0.00139 0.00056 2.62251
C*–H7 0.00378 0.01244 −0.00145 0.00228 0.00083 0.38867
N*–H8 0.00366 0.01264 −0.00151 0.00233 0.00083 0.27326
H10–N* 0.00413 0.01443 −0.00172 0.00266 0.00094 0.28853
C*–H8 0.00430 0.01434 −0.00173 0.00266 0.00093 0.53753
C*–H8 0.00276 0.00888 −0.00094 0.00158 0.00064 1.18349
C*–H7 0.00249 0.00778 −0.00083 0.00139 0.00056 2.62251
C*–H7 0.00378 0.01244 −0.00145 0.00228 0.00083 0.38867
C*–H5 0.00300 0.00999 −0.00105 0.00178 0.00072 1.09718
H6–C* 0.00185 0.00533 −0.00060 0.00097 0.00037 1.79163
C*–H6 0.00347 0.01180 −0.00133 0.00214 0.00081 1.29629
C*–H3 0.00326 0.01031 −0.00104 0.00181 0.00077 0.79912
C*–N2 0.00157 0.00383 −0.00047 0.00071 0.00024 0.66334
C*–N1 0.00186 0.00463 −0.00057 0.00086 0.00029 0.21374
C*–H1 0.00322 0.01052 −0.00105 0.00184 0.00079 1.16735
C*–H19 0.00111 0.00299 −0.00035 0.00055 0.00020 0.45049
C*–H19 0.00342 0.01108 −0.00113 0.00195 0.00082 1.25767
C*–H18 0.00428 0.01419 −0.00163 0.00259 0.00096 0.86843
N*–H16 0.00414 0.01407 −0.00169 0.00260 0.00092 0.21449

ρ—Electron density (a.u.) ; ∇2ρ—Laplacian of electron density (a.u); V(r)—Potential energy density (a.u.);
G(r)—Kinetic energy density (a.u.); H(r)—total energy density (a.u) and Ellipticity (εb) at the BCP
*For atom numbering see Scheme 1

[36]. The sign of Laplacian is determined by energy that
dominates in the bonding zone. A positive ∇2ρ indicates
that kinetic electron energy density G(r) is greater than
the potential electron energy density V(r). Such an interac-
tion is observed in closed shell systems or a noncovalent
interaction, where the depletion of electronic charge along
the bond path is observed [37]. A negative value of ∇2ρ at
BCP indicates a covalent bond. The positive value of H(r),
also indicate the existence of noncovalent interaction at the
BCP. The ellipticity is defined as ε = |𝜆1 |∕𝜆2 − 1. The ellip-
ticity provides a measure of π and σ bond character. The
larger values (>0.1) indicate a π character and lower values
shows the existence of σ bond character [38].
Our AIM calculations show the existence of
C–H⋯Metal and C–H⋯C intramolecular BCPs between
the DAO and host molecule. The charge density (ρ) lie in

13
J Incl Phenom Macrocycl Chem

Fig. 3  Molecular topography

analysis for DAO@Ag-Pillar-
plex and DAO@Au-Pillarplex
complexes. a, b Bond critical
points (BCP), c, d ring critical
points (RCP) and e, f cage
critical points (CCP). Intra-
molecular BCP’s are shown in
dotted lines

13
 J Incl Phenom Macrocycl Chem

the range of 0.0015–0.0087 and 0.0021–0.0091 a.u. for

Ag-Pillarplex and Au-Pillarplex respectively. These
observed ρ are close to the values observed in interac-
tions of cationic ionic liquids with amino acids [39].
Notice the ρ value is similar for both the host molecules.
The Laplacian of the charge density ∇2ρ for correspond-
ing bonds were all negative, indicating the presence of
covalent interaction between the DAO and host mol-
ecule. The negative sign on ∇2ρ indicates the depletion
of electronic charge along the bond paths and implies an
electrostatic nature of bonding. To confirm it, we have
computed the total electronic energy density function at
BCPs, which is related to G(r) and V(r) by the equation.
H(r) = G(r) + V(r)
where G(r) and V(r) are the kinetic energy density and
the potential energy density at the BCPs. The computed
kinetic energy density for the intermolecular BCPs were all
positive, while the potential energy density was all nega-
tive and are smaller in magnitude than the kinetic energy
density. Hence the total electron energy density for all the
intermolecular BCPs are positive and are close to zero.
Therefore, they can be classified under a category with
partially covalent and with a partial electrostatic in char- Fig. 4  EDA results of DAO@metal-Pillarplex, considering DAO as
acter. The computed intramolecular bond ellipticity values one fragment and metal-Pillarplex as another fragment for Au-Pillar-
are in the range of 0.0471–2.625 for DAO@Au-Pillarplex plex and Ag-Pillarplex
and 0.0415–3.569 a.u. for DAO@Au-Pillarplex. Most of
the intramolecular hydrogen—metal bonds have ellipticity Spectral analysis
values higher than one. The existence of ellipticity values
higher than 0.1 suggest that the involvement of a π char- Intermolecular bonding between donor–acceptor com-
acter and values lower than 0.1 advocate the presence of plexes, leads to structural changes, which can be identified
σ bond character in the intramolecular bonding’s. Fur- by the signatures in characteristic shifts in the vibrational
thermore, the ellipticity of DAO@Au-Pillarplex are much frequency, 1H and 13C NMR chemical shifts compared
higher than the DAO@Au-Pillarplex. Thus, it can be sug- to their constituent guest and host molecules [42, 43].
gested that the Au-Pillarplex have more π bond character Selected vibrational frequencies of DAO, metal-Pillarplex
towards the guest molecules [40]. and DAO@metal-Pillarplex are reported in Table 6. The
EDA analysis provides quantitate measurement, vibrational spectra for DAO, Au-Pillarplex and DAO@Au-
which would be useful to understand the nature of inter- Pillarplex are depicted in Fig. 5a–c. The vibrational spectra
action in these complexes [41]. The total binding ener- for Ag-Pillarplex and DAO@Ag-Pillarplex are provided in
gies are decomposed into ΔEdisp, ΔEPauli, ΔEelstat, and supporting information Fig. S5. In the Au-Pillarplex com-
ΔEorb terms. The results of the EDA analysis are given plex, the C–H stretching frequencies for the imidazole and
in Fig. 4. The ΔEPauli repulsive terms are nearly identical pyrazole appears as doublet (3238 and 3262 cm−1). The
for both the host molecules. On the contrary, the origin methylene hydrogens that exists between the imidazole has
of attractive interaction differs for Au-Pillarplex and Ag- a stretching frequency in range 3021–3087 cm− 1. As shown
Pillarplex guest molecule. The ΔEorb contribution and in Fig. 5a doublet (3392 and 3510 cm−1) of comparable
the ΔEelstat have an equal contribution towards attractive intensities are assigned to NH stretching for the isolated
forces in the inclusion complex formation process. The DAO. The methylene C–H stretching frequencies of the
dominant attractive contributor is the ΔEdisp term, which pristine DAO was observed in the region 2933–3027 cm−1.
is larger for Au-Pillarplex than the Ag-Pillarplex. Thus On complexation with Au-Pillarplex, the NH stretching fre-
Au-Pillarplex can be better host for linear molecules quency reveals a blue-shift of ∼39 cm−1 and was observed
than its counterpart Ag-Pillarplex. (Table 5). at 3549 cm−1. The symmetrical NH stretching frequency
was observed at 3420 cm−1. The C–H group on the imi-
dazole does not exhibit frequency down shift since this

13
J Incl Phenom Macrocycl Chem

Table 5  Topological BCP ρ −∇2ρ V(r) G(r) H(r) εb

parameters obtained from
AIM analysis for the DAO@ H117–Au4 0.00714 0.02082 −0.00333 0.00427 0.00094 0.04153
Au-Pillarplex
H57–Au2 0.00512 0.01493 −0.00222 0.00298 0.00076 0.16830
H57–Au6 0.00824 0.02510 −0.00409 0.00518 0.00109 0.09379
H118–Au7 0.00713 0.02177 −0.00338 0.00441 0.00103 0.17019
H118–Au3 0.00635 0.01881 −0.00291 0.00381 0.00089 0.01856
H116–Au3 0.00498 0.01459 −0.00196 0.00281 0.00084 3.14431
H56–Au1 0.00914 0.02707 −0.00465 0.00571 0.00106 0.02821
H119–Au5 0.00692 0.02071 −0.00319 0.00418 0.00099 0.08552
H58–Au8 0.00833 0.02498 −0.00409 0.00517 0.00108 0.04778
H56–N* 0.00370 0.01262 −0.00155 0.00235 0.00080 0.45107
N*–H117 0.00438 0.01515 −0.00187 0.00283 0.00096 0.20758
N*–H119 0.00355 0.01181 −0.00143 0.00219 0.00076 0.14517
N*–H58 0.00292 0.00956 −0.00116 0.00177 0.00062 0.07980
C*–H120 0.00460 0.01536 −0.00185 0.00284 0.00100 0.37355
C*–H59 0.00417 0.01433 −0.00169 0.00264 0.00095 0.74217
C*–H59 0.00312 0.01026 −0.00111 0.00184 0.00073 0.32234
N*–H60 0.00379 0.01394 −0.00174 0.00261 0.00087 3.25837
C*–H121 0.00328 0.01141 −0.00122 0.00204 0.00082 1.33964
C*–H121 0.00179 0.00504 −0.00054 0.00090 0.00036 0.74598
C*–N133 0.00201 0.00511 −0.00064 0.00096 0.00032 0.34997
C*–H142 0.00335 0.01126 −0.00113 0.00197 0.00084 1.27780
C*–H145 0.00210 0.00626 −0.00063 0.00110 0.00047 0.50304
C*–N132 0.00160 0.00404 −0.00049 0.00075 0.00026 0.46626
C*–H114 0.00397 0.01292 −0.00132 0.00228 0.00095 1.03962
C*–H53 0.00412 0.01308 −0.00141 0.00234 0.00093 1.07103
H54–C* 0.00242 0.00720 −0.00078 0.00129 0.00051 2.63972
N*–H54 0.00315 0.01129 −0.00134 0.00208 0.00074 4.57151
H55–C* 0.00327 0.01100 −0.00124 0.00199 0.00076 0.58568
H55–C* 0.00466 0.01394 −0.00180 0.00264 0.00084 3.86960
C*–H116 0.00292 0.00979 −0.00110 0.00177 0.00068 0.53125

ρ—Electron density (a.u.); ∇2ρ—Laplacian of electron density (a.u.); V(r)—Potential energy density (a.u.);
G(r)—Kinetic energy density (a.u.); H(r)—total energy density (a.u) and Ellipticity (εb) at the BCP
*For atom numbering see Scheme 1

functionality does not involve in the intramolecular inter-
actions. Due to the metal–CH interaction the methylene
C–H hydrogen in the DAO upon complexation exhibits a
shift to a lower wavenumber 2918 cm−1 in the DAO@Au-
Pillarplex complex. The methylene hydrogen close to the
NH group also experience a shift to a longer wavenumber
and was observed at 2990 cm−1, indicating the involvement
in the intramolecular bonding. Likewise, the complexation
of DAO with Ag-Pillarplex show a blue shift in the stretch-
ing frequencies of DAO upon complexation. Furthermore,
a relatively large frequency red-shift was observed for the
N–H stretching in Au-Pillarplex that its counterpart. Thus,
stronger interactions are experienced in Au-Pillarplex.
It is well known that the host–guest binding can be mon-
itored through 1H and 13C NMR experiments. GIAO com-
puted δH and δC values of the pristine DAO and those of
the inclusion complexes computed using the self-consistent
reaction field theory (SCRF) in acetonitrile solvent are
summarized in Tables 7 and S2 in the supporting informa-
tion. The 1H and 13C NMR spectra for DAO@Au-Pillarplex
and its constituents are shown in Fig. 6 and in the support-
ing information Fig. S7, DAO@Ag-Pillarplex and its con-
stituents are provided. The accurate determination of NMR
parameters is a challenging task and requires simulation of
electron correlation. It should be worth to specify that dis-
persion corrected functionals combined with the Huzinaga
and further extended correlated basis set have been carried
out for water clusters and clatherates [44]. Determining the
NMR spectral properties with such level of theory becomes
computationally demanding for large molecular systems.
We therefore employ B3LYP functional, which has been
widely used to study the metal complexes [45, 46].

13
 J Incl Phenom Macrocycl Chem

Table 6  Selected vibration DAO Ag-Pillarplex DAO@Ag-Pillarplex Au-Pillarplex DAO@Au-Pillarplex

frequencies in the DAO,
Ag-Pillarplex, Au-Pillarplex, ν(N–H) 3510, 3392 3553, 3547, 3429 3549, 3534, 3424
DAO@Ag-Pillarplex and
3424, 2999, 2997 3414
DAO@AuPillarplex
ν(CH) 3027, 3014 2995, 2987, 2962 3033, 3025, 3002
3003, 2991 2954, 2942, 2938 2993, 2990, 2970
2980, 2971 2930, 2905, 2900 2951, 2948, 2945
2966, 2942 2838, 2836 2943, 2928, 2918
2939, 2935 2907, 2846, 2838
2933
NH2 sci 1631 1644, 1642, 1490 1644, 1642
CH2 sci 1471, 1465 1485, 1478, 1470 1490, 1486, 1477
1458, 1450 1470
1443, 1440
CH2 wag 1350, 1347 1386, 1345, 1336 1380, 1334, 1307
1341, 1340 1310, 1295, 1282 1297, 1292, 1274
1318, 1289 1276, 1253,1242 1251, 1243, 1214
1280, 1261 1213, 1203, 1179 1204, 1175
1246, 1226
ν(C1′–H1′) 3260, 3259 3265, 3261, 3259 3262, 3260 3268, 3265, 3261
3237, 3235 3258, 3240, 3238 3238, 3236 3260, 3243, 3241
3236, 3234 3240, 3238, 3236
ν(C2′–H2′) 3214 3213 3217 3217, 3216
ν(C3′–H′) 3110, 3084 3110, 3108, 3084 3111, 3087 3111, 3109, 3086
3043, 3020 3082, 3041, 3030 3042, 3022 3084, 3042, 3041
3018 3020, 3018, 3017 3021

Table 7  NMR chemical shifts on the guest molecule for pristine

(a) DAO, DAO@Ag-Pillarplex and DAO@Au-Pillarplex in acetonitrile
solvent
Lig@Au-Pillarplex
Au-Pillarplex DAO DAO@Ag-Pillarplex DAO@Au-Pillarplex
Lig
Intensity (a.u)

N–H1 0.68 −1.04 −1.05

N–H2 0.68 0.01 0.01
(b) N–H3 0.68 −0.24 −0.24
N–H4 0.68 0.60 0.60
C1–H5 2.53 0.78 0.78
C1–H6 2.53 0.97 0.97
(c)
C2–H7 1.20 −1.12 −1.12
C2–H8 1.20 −1.39 −1.40
C3–H9 1.12 −0.41 −0.40
3500 3000 2500 2000 1500 1000 500 0
-1 C3–H10 1.12 −0.39 −0.39
Wavenumber (cm )
C4–H11 1.18 0.43 0.43
C4–H12 1.18 0.87 0.87
Fig. 5  Computed vibrational spectra of (a) DAO molecule (b) Au- C5–H13 1.18 1.30 1.30
Pillarplex and (c) DAO@Au-Pillarplex
C5–H14 1.18 1.53 1.53
C6–H15 1.12 0.23 0.23
C6–H16 1.12 0.41 0.41
The protons in the DAO are classified as the amino pro-
C7–H17 1.20 −0.74 −0.75
ton (H1–H4) and protons from the methyl group (H5–H20).
C7–H18 1.20 −1.17 −1.18
All protons on the guest molecules upon complexation
C8–H19 2.53 −0.13 −0.13
experience a larger upfield shift upon complexation, as the
C8–H20 2.53 0.01 0.01
guest molecule has metal core which increase the electron

13
J Incl Phenom Macrocycl Chem

Fig. 6  Computed. a 1H NMR spectra Au-Pillarplex. b 1H NMR spectra DAO molecule. c 1H NMR spectra DAO@Au-Pillarplex. d 13
C NMR
spectra Au-Pillarplex. e 13C NMR spectra DAO molecule and f 13C NMR spectra of DAO@Au-Pillarplex in acetonitrile solvent

density on the guest molecule though its lone pair of elec-
trons. The H1 and H3 proton which are in bonding with the
imidazole group reveals a large upfield compared to the H2
and H4 protons on the amino group which are non-interact-
ing with the guest molecule. The alkyl protons which are in
close proximity to the imidazole fragment of the guest mol-
ecules experience a larger upfield shift that those which are
away. Furthermore, the proton which are closer to the metal
sites experience larger shielding possibly due to C–H→LP*
Metal interaction.
The shielding effect on the DAO has been studied using
the 13C NMR and the data obtained are reported in Table S2
in the supporting information. The computed 13C NMR
spectra is provided in the Figs. 6 and S6. In the DAO mol-
ecule, due to symmetry C1 and C8 carbons shows signal at
49 ppm. The C4 and C5 carbon which are at the middle of
the ligand and are isoelectronic and show signal at 38 ppm.
Upon complexation, C5 experience a high upfield shift
which was attributed to the C–H···Metal interaction and
was observed at 45 ppm. Furthermore, on complexation the

13

degeneracy in the 13C NMR signal of DAO is lost, and one
end is more deshielded than the other end. Lastly the 15N
signal observed for the DAO has signal at 220 ppm which
is nearly identical to that observed for the DAO@metal-Pil-
larplex. This indicates that metal centers in the host plays a
vital role in stabilizing the ligand than the terminal amines.
Conclusion
Systematic investigation on metal-Pillarplex (metal = Cu,
Ag and Au) and its inclusion complex with 1,8-diami-
nooctane have been carried out using dispersion corrected
density functional theory. The following conclusions are
drawn.
1. The coordinated metal atoms tune the cavity size and
the height of metal-Pillarplex and form a rigid cavity
thereby reducing their structural deformation. Linear
molecules are more stabilized inside the cavity than
their isomers.
2. Cu-Pillarplex undergoes a large deformation both on
the host and guest molecule, as the guest molecule
undergoes chemisorption. On the contrary, Ag and Au-
Pillarplex forms inclusion complex by physical adsorp-
tion.
3. The calculated Gibbs free energy for the formation of
inclusion complex were negative indicating their facile
formation at the room temperature. Computed binding
energies with various functionals and energy decom-
position analysis, shows that dispersion correction is
essential in these systems.
4. The low binding energy, and the physical adsorption
of guest molecule and HOMO–LUMO spatial diagram
indicates, that the Au and Ag-Pillarplex can be used as
reversible host for linear alkanes.
5. Complexation of guest engenders frequency shift in
the vibrational spectra. Calculated 1H NMR reveal that
guest protons which are closer to the metal sites experi-
ence larger shielding possibly due to C–H→LP* Metal
interaction. The 15N signal observed for the DAO is
nearly identical to that observed for the DAO@metal-
Pillarplex.
6. NBO and AIM analysis indicate that metal centers in
host, play a major role in stabilizing the guest inside
the cavity than the amino group on the guest molecule.
Acknowledgements NSV thank the SERB-DST, India for funding
through a project (EMR-II-SB/S1/PC-047/2013). The authors grate-
fully acknowledge the Center for Computational Materials Science at
the Institute for Materials Research for use of the Hitachi SR16000
(Model M1) supercomputer system. The authors also register their
thanks to CDAC-pune for providing computational resource through
13
J Incl Phenom Macrocycl Chem
the PARAM Yuva II system. SA thank the SERB-DST, India for
funding through a project with sanction No. SB/FT/CS-038/2013.
Compliance with ethical standards
Conflict of interest The authors declare that they have no conflict
of interest.
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