Guest-Induced Structural Transformations in a Porous Halogen-Bonded Framework

Article abstract of DOI:10.1002/anie.201806399

Structural evidence obtained from in situ X-ray diffraction shows that halogen bonding is responsible for the formation of a dynamic porous molecular solid. This material is surprisingly robust and undergoes reversible switching of its pore volume by activation or by exposure to a series of gases of different sizes and shapes. Volumetric gas sorption and pressure-gradient differential scanning calorimetry (P-DSC) data provide further mechanistic insight into the breathing behavior.

Full text of DOI:10.1002/anie.201806399

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Accepted Article
Title: Guest-induced structural transformations in a porous halogen
bonded framework.
Authors: Leonard Barbour, Varvara Nikolayenko, Dominic Castell, and
Dewald van Heerden
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201806399
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Guest-induced structural transformations in a porous halogen
bonded framework.
Varvara I. Nikolayenko, Dominic C. Castell, Dewald P. van Heerden and Leonard J. Barbour*
Abstract: Structural evidence obtained from in situ X-ray diffraction
shows that halogen bonding is responsible for the formation of a
dynamic porous molecular solid. This material is surprisingly robust
and undergoes reversible switching of its pore volume by activation or
by exposure to a series of gases of different sizes and shapes.
Volumetric gas sorption pressure-gradient differential scanning
calorimetry (P-DSC) data provide further mechanistic insight into the
breathing behavior.
activation in the form of a permanently porous material. Herein,
we describe a flexible, permanently porous organic XB framework
(Scheme 1) that survives activation without framework collapse.
Moreover, the material responds to gas loading (carbon dioxide,
methane, ethane, propane and butane) under pressure by
adapting its guest-accessible space according to the geometry of
the guest molecule.
Slow evaporation of a solution of 1,2-bis(2'-methyl-5'-(pyrid-
4''-yl)thien-3'-yl)perflourocyclopentene and 1,4-di-iodotetrafluoro-
benzene (halogen bond acceptor XBA and donor XBD,
respectively, see Scheme 1) in acetone afforded yellow crystals,
one of which was subjected to single-crystal X-ray diffraction
(SCD) analysis at 100 K. The asymmetric unit consists of one
molecule each of XBA, XBD and acetone, which pack in the
space group Pna21 to form a solvate 1a. Compounds XBA and
XBD are arranged end-to-end as sinusoidal (XBA···XBD···)n
halogen bonded chains, involving I···N interactions (Figure S2),
that propagate along [302] and [30-2].
Porous materials hold remarkable potential for gas storage[1] and
separation,[2] drug delivery,[3] molecular recognition[4] and
catalysis,[5] among others. In recent years the field has been
dominated by coordination polymers,[6] metal organic frameworks
(MOFs),[7] hydrogen bonded organic frameworks (HOFs)[8] and
covalent organic frameworks (COFs).[9] Despite the abundance of
reports on these types of porous materials, the search for new
and alternative methods to generate porosity in the solid-state is
still a highly topical area of research.[10]
Porous molecular solids constitute a distinct class of materials
that possess intrinsic[11] or extrinsic[12] voids, or even both types
simultaneously,[13] that are accessible to guest molecules by
means of diffusion. Intrinsic porosity occurs when host molecules
contain guest-accessible cavities that preclude close-packing.
Extrinsic pores consist of interstitial spaces between host
molecules, and are generally due to awkward packing of the host.
While many porous molecular solids contain open channels, it has
Scheme 1 The molecular structures of XBA and XBD.
been demonstrated that permanent channels are not
a
prerequisite for porosity.[11a] In such systems, concerted dynamic
processes occur within the host structure that facilitate diffusion
of guests via transient channels.
It is useful for subsequent structural discussions to consider
chains aligned in a given direction as packing side-by-side to form
planes parallel to (010); adjacent chains are offset relative to each
other by a phase angle of 120° such that each plane consists of
chains stacked in an (ABC)n manner (Figure 1).
The halogen bond (XB) is defined as a directional noncovalent
attractive interaction between a Lewis base (XB acceptor) and a
polarized halogen atom (XB donor).[14] To date, the XB has been
used to prepare a wide range of complex supramolecular
assemblies and functional materials.[15] While interesting from a
structural perspective, they also have appealing chemical
properties. A few examples include rotaxanes,[16] molecular
capsules,[17] organic cages[18] and light-responsive materials.[19]
Several separate reports[20] have described XB molecular solids
that exhibit dynamic porosity. However, in all of these cases,
guest inclusion occurs via solvent exchange – i.e., exposure of a
crystalline solvate to the vapor of a different solvent. None of
these reports demonstrate that the host framework can survive
Figure 1 Perspective view of sinusoidal (XBA···XBD···)n halogen bonded
strands propagating along [30-2]. Neighboring strands are offset relative
to each other and stack parallel to (010) in an (ABC)n manner. Molecules
are shown in spacfilling representation with A, B and C strands shown in
red, green and blue, respectively.
We note that the strands comprising each layer do not form a
weave (Figure S3). Successive planes alternate with respect to
the direction of their strands such that a crisscross pattern is
formed (Figure S4). A map[21] of the guest-accessible surface
indicates that the acetone guest molecules are located between
the layers in undulating channels that extend along [010] (Figure
2, top). Two of these channels traverse a unit cell, and each has
a guest-accessible volume of 247 Å3 per unit cell, as determined
[a]
Dr V. I. Nikolayenko, Dr D.C. Castell, Mr D. P van Heerden and
Professor L. J. Barbour
Department of Chemistry and Polymer Science
University of Stellenbosch
Stellenbosch 7600, South Africa
E-mail: ljb@sun.ac.za
Electronic Supplementary Information (ESI) available: Experimental details,
SCXRD, PXRD, TGA, volumetric gas sorption analysis, P-DSC, VT-PXRD
and molecular mechanics calculations. CCDC 1846617-1846624
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using a spherical probe of radius 1.5 Å (Figure S5). This equates
to a guest-accessible volume of 124 Å3 per guest binding site
(Table 1).
thermal stability,[24-25] improved gas affinity,[24] and potential
catalytic activity.[23]
To the best of our knowledge, 1 represents the first example
of a porous halogen bonded framework that can be activated.
Comparison of 1a and 1apo suggests that 1apo might adapt
dynamically in the presence of a range of suitable guests to regain
the expanded host structure. Moreover, the material appears to
tolerate significant structural contraction as a single-crystal to
single-crystal (SC-SC) transformation. We are therefore
presented with a rare opportunity to carry out a series of
guest-loading structural studies (using an environmental gas cell
during SCD analysis)[11c] to complement sorption experiments.
To probe the porosity of 1apo, a series of gas sorption
experiments was carried out at 298 K using carbon dioxide,
methane, ethane, propane and butane (Figures 3 and 4). The bulk
sample was exposed to a maximum pressure of 20 bar (a
limitation of the instrument) in the cases of carbon dioxide,
methane and ethane, while maximum pressures of 7 and 2 bar
were reached for propane and butane, respectively (see ESI for
more detail). 1apo exhibits type I sorption behavior for CO2,
absorbing one guest molecule per host formula unit (HFU) at 20
bar. Type I sorption is also observed for methane, but with only
0.3 guest molecules included per HFU at 20 bar. Negligible
hysteresis upon desorption indicates minimal host-guest
interactions for both CO2 and CH4.
Figure 2 Surface maps of the guest-accessible space (probe radius = 1.5
Å) in 1a and 1apo as viewed along [010].
Table 1. Guest-accessible volumes for the as-synthesized, activated and
gas-loaded structures.
Structure
Guest
Pressure
/ bar
Volume per
guest
binding sitea
/ Å3
% Guest
accessible
volume per
HFU
1a
1apo
01apo
201c
201m
201e
71p
acetone
-
-
124
48
13.7
5.3
-
-
2.76 x 10-2
55
6.2
CO2
CH4
C2H6
C3H8
C4H10
20
20
20
7
55
7.1
58
6.6
143
151
156
15.4
16.1
16.4
21b
2
a Guest-accessible volume determined using Mercury[21-22] (probe radius 1.5
Å, grid spacing 0.2 Å). Owing to the multiplicity of binding sites in Pna21, the
volume per unit cell was divided by 4 in each case.
0
Figure 3 Volumetric gas sorption isotherms of 1apo exposed to CO2
Thermogravimetric analysis (TGA) of 1a (Figure S10)
indicates that the acetone guest can be removed between 100
and 113 °C. However, attempts to activate single crystals by
heating to this temperature resulted in loss of single crystallinity.
Therefore, a milder activation method was employed, involving
exposure of crystals to supercritical carbon dioxide (scCO2) for 30
minutes (see ESI). Apart from the appearance of minor cracks,
the crystals remained intact. SCD analysis at 100 K revealed that
(circles) and methane (diamonds). All isotherms where recorded at 298 K.
Shaded and open symbols represent absorption and desorption,
respectively.
the acetone had been removed to yield the apohost form 1apo
,
also in Pna21. The most notable structural change upon activation
involves the shape and volume of the guest-accessible space –
the channels shrink to become discrete voids (Figure 2, bottom),
with an overall reduction in guest-accessible volume from 124 to
48 Å3 per guest binding site. Bulk phase activation of the material
was confirmed by TGA (Figure S10). The guest-accessible space
is partially delimited by fluorine atoms of XBA, thus presenting a
potentially interesting environment for further host-guest
chemistry. Indeed, some materials with fluorine-lined guest-
accessible cavities have been shown to possess several
favorable sorption properties[23] such as higher oxidative and
0
Figure
4
Volumetric sorption isotherms of 1apo exposed to ethane
(triangles), propane (squares) and butane (circles). In all cases the
isotherms exhibit hysteresis, with propane and butane retained at vacuum.
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The ethane sorption isotherm shows an inflection at
approximately 1.5 bar, and reaches a total guest occupancy of
half a molecule per HFU at 20 bar. This type of stepped isotherm
implies a gate-opening mechanism. In the case of propane, half a
guest molecule per HFU is absorbed between 0 and 1 bar, with
the occupancy reaching 0.9 at the saturation pressure of 7 bar.
The desorption isotherm shows hysteresis, with the material
retaining 0.35 molecules per formula unit at vacuum. Butane is
absorbed in a similar manner, with the inclusion of half a guest
molecule at the saturation pressure limit of 2 bar. Desorption
again occurs with hysteresis, with the retention of almost 0.5
molecules of butane at vacuum.
To gain structural insight into the modes of guest inclusion
for the different gases at 298 K, SCD analyses were carried out
for gas-loaded crystals at the same temperature. A crystal of 1apo
was mounted in an environmental gas cell, which was then
evacuated and sealed before SCD data were recorded for the
activated material under vacuum (01apo).
The volume of each guest-binding site of 01apo (Figure 5a) is
approximately 55 Å3, which is consistent with thermal expansion
of 1apo. The lengths of the two unique N···I halogen bonds are
d(N···I) = 2.88(1) and 2.85(1) Å, which are approximately 20%
shorter than the sum of the van der Waals radii[26] of the
interacting atoms. Typical of directional XB interactions,[15] the
N···I–C bond angles of 177.0(5)° and 177.5(5)°, respectively, are
almost linear. Examination of intermolecular interactions using
CrystalExplorer[27] shows that there are no notable intermolecular
interactions, apart from the abovementioned N···I halogen bonds
(Video S1). However, there are relatively weak CH···F hydrogen
bonds with d(C···F) = 3.35(2) Å between layers. The wavelength of
the sinusoidal chains is 53.9 Å (Figure S6).
Subsequent SCD experiments were undertaken as follows,
starting with a new crystal of 1apo in each case. After backfilling
0
the environmental cell with gas to the maximum pressure
recorded for the corresponding isotherm, the system was left to
equilibrate for 12 h before being sealed. SCD data were then
recorded for the gas-loaded crystal x1g, (x = pressure in bar, g =
c, m, e, p and b for carbon dioxide, methane, ethane, propane
and butane, respectively). In each case the guest molecule was
either modelled crystallographically (methane and ethane), or by
means of molecular mechanics (carbon dioxide, propane and
butane) using Materials Studio[28] (Figure 6 and ESI). In all cases
the guest occupancy was confirmed using residual electron
density analysis, as implemented by the SQUEEZE[29a] routine of
PLATON.[29b] We note that, even when the guest cannot be
modelled crystallographically, in situ gas loading diffraction data
provide valuable information with regard to the guest-accessible
space, as well as a reliable host model for theoretical simulations.
SQUEEZE analysis of 201c indicated the presence of one
molecule of CO2 per HFU, which is consistent with the sorption
data. The low guest occupancy of 0.3 molecules of methane per
HFU for 201m also corresponds with the gas sorption data. The
structural models show that the modes of guest inclusion are
similar for carbon dioxide and methane, and that little distortion of
0
the guest-accessible space of 1apo is required to accommodate
these gases. Relative to 01apo, guest uptake results in only modest
increases in the guest-accessible volumes by 13.6% and 4.5% in
201c and 201m, respectively. This is likely due to excellent
Figure 6 A perspective view along [010] of the gas-loaded structures with the
guest-accessible space shown as semi-transparent surfaces.[22] Theoretically
determined guest positions are shown for 201c, 71p and 21b.
Figure 5 Packing diagrams viewed down [001] with a) showing the
0
CH···F hydrogen bonding and discrete cavities in 1apo and b) showing
the channels in 201e.
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size-shape complementarity between these guest molecules and
the guest-accessible pockets, as inferred from diffraction analysis
and molecular mechanics calculations. The packing coefficients
of CO2 and CH4 (i.e. ratio of molecular volume to available space)
are 55% and 49%, respectively. Indeed, CO2 is a particularly
suitable van der Waals guest since its packing coefficient is
strikingly consistent with that proposed by Rebek for optimal
binding of guests in host capsules (albeit in solution).[30] This
implies that a larger or more awkwardly shaped guest might either
not be included, or would require the host to undergo a structural
change. In the cases of CO2 and CH4, guest diffusion occurs
despite the absence of permanent pores, but the lack of a net
structural transformation accounts for the smooth type I isotherms
for these two gases.
In summary, we have presented the first example of a
porous halogen bonded framework that can be activated. Using a
combination of gas sorption, in situ single-crystal X-ray diffraction
and P-DSC experiments we have elucidated the dynamic
behavior of this porous molecular material upon exposure to guest
molecules of different sizes. Furthermore, we have provided an
explanation for this dynamic behavior based on structural data.
We believe that the halogen bond provides sufficient directionality
such that the breathing behavior can occur by means of lateral
sliding of XB layers relative to one another. To date, this type of
framework flexibility has not been reported for halogen-bonded
networks, and it is therefore of considerable value to use in situ
SCD data to propose a mechanism for the breathing effect. Finally,
diarylethenes are well known to undergo efficient photo-induced
structural switching in the solid state,[32] and our ongoing efforts
are aimed at furthering this work by developing a permanently
porous XB framework with light-modulated porosity.
0
Exposure of 1apo to 20 bar of ethane induces a SC-SC
transformation[31] to 201e (Figures 5b). The discrete voids expand
upon guest uptake to once again become open 1D channels
propagating along [001]. Indeed, the host of 201e reverts to a
structure that is isoskeletal[31] to that of 1a, with a pore volume of
143 Å3 per guest binding site (Table 1). Absorption of ethane
causes adjacent layers to move apart by ca 0.83 Å and
concomitantly slide laterally relative to one another by ca 2.3 Å
(Video S2). An analogous translation of layers has previously
been reported for a seemingly nonporous dynamic molecular
solid.[11a] Interestingly, a structural overlay (Figure S7) shows that
there is little change within each (ABC)n layer relative to that of
01apo; the wavelength of the sinusoidal chain is 54.3 Å, which
represents an increase of only 0.7% (Figure S6). The lengths of
the two unique N···I halogen bonds remain approximately the
Acknowledgements
We acknowledge the National Research Foundation of South
Africa for financial support.
Keywords: halogen bonding • dynamic• single-crystal to
single-crystal transformation • sorption • P-DSC
0
same as those of 1apo, with d(N···I) = 2.89(2) and 2.81(1) Å.
However, lateral sliding of adjacent layers involves breaking of the
weak CH···F hydrogen bonds, as confirmed by CrystalExplorer
(Video S3). Similar structural changes due to gate-opening are
observed for 71p and 21b, which implies that guests that are larger
or less awkwardly shaped than CO2 and CH4 induce breathing in
the apohost phase. The structural changes observed in the SCD
correlate well with the stepped isotherms for 1e-1b. The retention
of small amounts of propane and butane at vacuum indicates
potential host-guest interactions
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This article is protected by copyright. All rights reserved.

10.1002/anie.201806399
Angewandte Chemie International Edition
COMMUNICATION
COMMUNICATION
In situ single crystal X-ray
diffraction was used to
Varvara I. Nikolayenko,
Dominic C. Castell, Dewald P.
van Heerden and Leonard J.
Barbour*
study
bonded framework. This
material undergoes
a robust halogen
Page No. – Page No.
reversible switching of its
pore volume by activation
or by exposure to a series
of gases of different sizes
and shapes.
Guest-induced structural
transformations in a porous
halogen bonded framework.
This article is protected by copyright. All rights reserved.