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Linear Supramolecular Polymer Driven by Br⋅⋅⋅Br and Br⋅⋅⋅H Non-bonding Interactions Based on Inclusion-Complex of Octabromo-Functionalized Pillar[a]rene

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Mickey Vinodh
Mickey Vinodh
Mickey Vinodh
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Talal Alazemi at Kuwait University
Talal Alazemi
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Abstract and Figures

Co-crystal structure of inclusion complex based on macrocyclic host of octabromo-functionalized pillar[5]arene (PilBr8) and guest 1-bromooctane (OctBr) molecule is discussed. The host-guest interactions are achieved by efficient C–H⋅⋅⋅O and C–H⋅⋅⋅π nonbonding interactions. The packing pattern of the crystal structure shows the inclusion-complex [PilBr8⊃OctBr] formed one-dimensional supramolecular polymer network driven by Br⋅⋅⋅H and Br⋅⋅⋅Br non-bonding interactions. Hirshfeld surface analysis revealed that the guest molecule plays an important role in formation of self-assembled linear supramolecular polymer trough head-to-tail halogen bond (Br⋅⋅⋅H). Graphical Abstract Co-crystal of inclusion complex based on bromo-functionlized pillar[5]arene with 1-bromooctane displays the assembly of linear supramolecular polymer promoted by halogen-bonding interactions.
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Journal of Chemical Crystallography (2022) 52:399–406
https://doi.org/10.1007/s10870-022-00936-2
ORIGINAL PAPER
Linear Supramolecular Polymer Driven byBr⋅⋅⋅Br andBr⋅⋅⋅H
Non‑bonding Interactions Based onInclusion‑Complex
ofOctabromo‑Functionalized Pillar[a]rene
MickeyVinodh1· TalalF.Al‑Azemi1
Received: 15 April 2020 / Accepted: 4 March 2022 / Published online: 22 March 2022
© The Author(s), under exclusive licence to Springer Science+Business Media, LLC, part of Springer Nature 2022
Abstract
Co-crystal structure of inclusion complex based on macrocyclic host of octabromo-functionalized pillar[5]arene (PilBr8)
and guest 1-bromooctane (OctBr) molecule is discussed. The host-guest interactions are achieved by efficient C–H⋅⋅⋅O and
C–H⋅⋅⋅π nonbonding interactions. The packing pattern of the crystal structure shows the inclusion-complex [PilBr8⊃OctBr]
formed one-dimensional supramolecular polymer network driven by Br⋅⋅⋅H and Br⋅⋅⋅Br non-bonding interactions. Hirshfeld
surface analysis revealed that the guest molecule plays an important role in formation of self-assembled linear supramolecular
polymer trough head-to-tail halogen bond (Br⋅⋅⋅H).
Graphical Abstract
Co-crystal ofinclusion complex based on bromo-functionlized pillar[5]arene with1-bromooctane displays the assembly of
linear supramolecular polymer promotedby halogen-bonding interactions.
Keywords Pillararenes· Halogen-bonding· Host-guest system· Supramolecular polymer· Hirshfeld surface analysis
Introduction
Supramolecular polymers have gained considerable atten-
tion due to their interesting properties such as the ease of
association and dissociation, as well as stimuli-responsive-
ness [1–6]. Utilization of reversible non-covalent interac-
tions such as hydrogen-bonds, metal-ligand interactions,
host guest interactions, π–π interactions and van der Waals
forces are an important factor for controlled self-assembly
or self-organization of monomeric units leading to efficient
supramolecular polymers having intriguing properties. As
a result, synthesis of monomeric synthons and high con-
trol over molecular interactions among them to generate
novel supramolecular polymeric materials is a challenging
research area which demands careful design and feasible
reaction pathways. Macrocyclic molecules such as crown
ether, cyclodextrins, calixarenes, cucurbiturils are attractive
synthons for constructing supramolecular polymers due to
their structural tunability and high binding affinity to guest
molecules [7–11].
* Talal F. Al-Azemi
t.alazemi@ku.edu.kw
1 Chemistry Department, Kuwait University, P.O. Box5969,
13060Safat, Kuwait
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
... Pillararene systems containing substituted halogen atoms in their outer rims are of especial interest in the field of supramolecular chemistry because these types of halogen-containing macrocycles can selfassemble into a supramolecular network by halogen-halogen and/or halogen-hydrogen interactions. Supramolecular host-guest systems constructed by such halogen-based noncovalent interactions have drawn considerable interest in recent years [6][7][8][9][10][11][12][13][14][15][16][17][18][19][20]. Heaver halogens, particularly bromo and iodo derivatives, have been widely utilized in the assembly of such systems because they exhibit electrophilic characteristics and can interact with electron-pair-donating heteroatoms (O, N, S) or anions because of the anisotropic distribution of the electrostatic potential around the atomic center. ...
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