Non-Covalent Interactions Behind the Anion Recognition:

Bonding Situation in Metalated Calixarene Hosts

Alexandre O. (PG), Ina Ortolan 1?
(PG), Giovanni F. (PQ), Øestrøm 1 Caramori 1
2 3
Renato L.T. Parreira (PQ), Alvaro Muñoz-Castro (PQ), F. Matthias Bickelhaupt 4,5
(PQ).
1
Universidade Federal de Santa Catarina, Florianópolis, Brazil. 2 Universidade de Franca, Franca, Brazil. 3 Universidad
Autonoma de Chile, Santiago, Chile. 4 Vrije Universiteit Amsterdam, Amsterdam, The Netherlands. 5 Radboud University,
Nijmegen, The Netherlands.
?
alexandre.osmar@posgrad.ufsc.br

KS-MO/EDA analysis, the molecular electro- reinforced by donor-acceptor interactions be-

1. Introduction
static potential maps (MEPs), the Hirshfeld tween the guest’s HOMO and the empty π ∗-
Non-covalent interactions (NCI) are the pri- and NPA charge analysis were also computed type orbitals in the calixarene bowl (Fig. 3).
mary forces involved in the recognition, trans- at the same level of theory.7
port, and regulation of many events in bio-
1
logical systems. Although the critical role of ∆Eint = ∆Velstat + ∆EPauli + ∆Eoi + ∆Edisp -2.48 LUMO+2 LUMO+3

anionic molecules is well known, the chem- -2.51

E ~
LUMO+1

istry of anion receptors is still a growing area.2 (eV) ~

-3.50
For instance, the anion–π interactions in a se- 3. Results and Discussion -3.54
LUMO+2
LUMO LUMO+1

ries of heterocalixarenes hosts were recently

3,4 -3.70
addressed by us. In this connection, At- Table 1: Energy Decomposition Analysis 2px 2py 2pz
~
wood and co-workers5 reported the synthe- (kcal mol−1) for the host-guest complexes ~
-4.36
– – – – – –
sis and characterization of a series of macro- 1·X (X = Cl , Br and I ) and 1·BF4 – HOMO

-4.42
–
cyclic complexes based on calix[4]arene and its 8·BF4 . shifted -4.34 eV
HOMO-2 HOMO-1
shifted +1.49 eV

derivatives, water-soluble and air-stable, pos- Cl- 1·Cl- 1

∆Eint ∆Eprep ∆EPauli ∆Velstat ∆Eoi ∆Edisp
sessing an inner hydrophobic cavity suitable 1·Cl – -77.5 6.1 45.2 -68.5 (56%) -40.3 (33%) -14.1 (11%)
to incorporate anionic species via noncova- 1·Br – -78.0 12.0 54.9 -78.4 (59%) -37.0 (28%) -17.5 (13%) Figure 3: Orbital-interaction diagram for
1·I – -73.8 11.3 61.3 -81.6 (60%) -31.3 (23%) -22.2 (16%) –
lent interactions.5,6 Their host capability was 1·BF4 – -67.0 11.9 29.5 -56.0 (58%) -25.1 (26%) -15.4 (16%)
complex 1·Cl , based on KS-MO analysis.
confirmed by X-ray crystallography in recog- 2·BF4 – -57.0 3.9 34.5 -51.8 (57%) -24.2 (26%) -15.5 (17%)
3·BF4 – -45.8 1.9 28.4 -38.8 (52%) -22.2 (30%) -13.2 (18%)
nizing BF− 4 , SO 2−
4 , and I −6
. Based on these 4·BF4 – -27.8 2.8 29.9 -21.6 (37%) -22.5 (39%) -13.6 (24%)
5·BF4 – -15.0 1.4 22.2 -1.0 (3%) -22.4 (60%) -13.8 (37%)
host-guest complexes (Fig. 1) we performed 6·BF4 – -50.0 3.0 31.5 -40.7 (50%) -25.1 (31%) -15.7 (19%)
4. Conclusions
a comprehensive electronic-structure analysis 11
7·BF4 – -39.1 2.9 24.4
12
-26.8 (42%) -22.7 (36%)
13
-14.0 (22%)
8·BF4 – -28.0 1.8 20.0 -13.7 (29%) -21.0 (44%) -13.3 (28%) Our results highlight the enormous anion-
of the physical nature of the noncovalent inter- MOLECULAR ELECTROSTATIC POTENTIAL recognition capability of organometallic cal-
actions involved in anion recognition in met-
ixarenes. We envisage that this will encourage
alated calix[4]arene hosts at DFT-D level of
7
14 15 16
attempts to rationally design and synthesize
theory.
+0.200,200 highly selective hosts.
0,060 0,50

0,148 -0,005 0,25

1 2 3 4 0,095 -0,070 0,00

0,043

-0,010
-0,135

-0,200
5. Acknowledgements
-0,25

-0,50

-0.01
17 18

1·Cl
-
1·Br
-
1·I
- 5 6 7 8
AOO and GFC thanks CNPq (grants
Figure: MEP on the electron density isosurface (0.01 u.a.). 
 142339/2015-6 and 311963/2017-0), IØ and
Color scale shown in Hartree.

Figure 2: Molecular electrostatic potential 11

RLTP thanks CAPES (grants 1732086
maps of host structures 1–8. and 88881.068346/2014-01). RLTP thanks
1·BF4
-
2·BF4
-
3·BF4
-
FAPESP (grant 2011/07623-8). AMC thanks
7 FONDECYT (grant 1180683). FMB thanks
Our results reveal that the anion–π inter-
NWO.
actions are strengthened and can be effi-
4·BF4
-
5·BF4
-
6·BF4
- ciently tuned through the proper choice of
6. References
the exo-coordinating metal fragment to the
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more, the guest’s steric fit in the host frame-
7·BF4
-
8·BF4
- [2] Lehn, J. M. Supramolecular Chemistry. 1995, Wiley-VCH,
work is a selective and crucial criterion for Weinheim, Germany.
the anion recognition. The fit of small an- [3] Ortolan, A. O.; Caramori, G. F.; Bickelhaupt, F. M.; Parreira,
Figure 1: Optimized structures of all ions occurs with less geometrical deforma- R. L. T.; Muñoz-Castro, A.; Kar, T. Phys. Chem. Chem. Phys.
host-guest complexes at ZORA-BP86- 2017, 19, 24696-24705.
tion of the host cavity and thus less destabi-
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lizing deformation strain upon accommodat- da Silva, E. H.; Bickelhaupt, F. M. J. Phys. Chem. A. 2018,
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[6] Staffilani, M.; Hancock, K. S. B.; Steed, J. W.; Holman, K. T.;
All calculations were performed at ZORA- complexed hosts, followed by technetium and Atwood, J. L.; Juneja, R. K.; Burkhalter, R. S. J. Am. Chem.
BP86-D3(BJ)/TZ2P level of theory at ADF molybdenum macrocyclic receptors (Fig. 1). Soc. 1997, 119, 6324-6335.

2016 software.7 The non-covalent interactions
were investigated by employing Kohn-Sham
molecular orbital (KS-MO) theory in con-
junction with a canonical energy decomposi-
tion analysis (EDA).8 To give support to the
The coordinated metals provide a substantial [7] Ortolan, A. O.; Østrøm, Ina; Caramori, G. F.; Parreira, R.
L. T.; Muñoz-Castro, A.; Bickelhaupt, F. M. Organometallics
electrostatic stabilization to anion recogni- 2018, 37, 2167-2176.
tion, making the calixarene cavity a more elec- [8] Bickelhaupt, F. M.; Baerends, E. J. Kohn-Sham Density
tron deficient and turning it into a stronger Functional Theory: Predicting and Understanding Chemistry.
In: Reviews in Computational Chemistry. 2000, Wiley-VCH:
π-acid (Fig. 2). The interaction is further New York, 15, 1-86.

IV EQC, Ribeirão Preto: 2018