Supramolecular Alloys from Fluorinated Hybrid Tri4Di6 Imine Cages

Article abstract of DOI:10.1002/chem.202100891

To create innovative materials, efficient control and engineering of pore sizes and their characteristics, crystallinity and stability is required. Eight hybrid Tri⁴Di⁶ imine cages with a tunable degree of fluorination and one fully fluorinated Tri⁴Di⁶ imine cage are investigated. Although the fluorinated and the non-fluorinated building blocks used herein differ vastly in reactivity, it was possible to gain control over the outcome of the self-assembly process, by carefully controlling the feed ratio. This represents the first hybrid material based on fluorinated/hydrogenated porous organic cages (POCs). These cages with unlimited miscibility in the solid state were obtained as highly crystalline samples after recrystallization and even showed retention of the crystal lattice, forming alloys. All mixtures and the fully fluorinated Tri⁴Di⁶ imine cage were analyzed by MALDI-MS, single-crystal XRD, powder XRD and in regard to thermal stability (TGA).

Full text of DOI:10.1002/chem.202100891

Accepted Article
Accepted Article
Title: Supramolecular Alloys From Fluorinated Hybrid Tri4Di6 Imine
Cages
Authors: Tom Kunde, Tobias Pausch, and Bernd M. Schmidt
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Chem. Eur. J. 10.1002/chem.202100891
Link to VoR: https://doi.org/10.1002/chem.202100891
0
1/2020

Chemistry - A European Journal
10.1002/chem.202100891
COMMUNICATION
4
6
Supramolecular Alloys From Fluorinated Hybrid Tri Di Imine
Cages
‡
‡
*
Tom Kunde, Tobias Pausch and Bernd M. Schmidt
[a]
Tom Kunde, Tobias Pausch and Dr. Bernd M. Schmidt
Institut für Organische Chemie und Makromolekulare Chemie
Heinrich-Heine-Universität Düsseldorf
Universitätsstraße 1, D-40225 Düsseldorf, Germany
E-mail: Bernd.Schmidt@hhu.de
Homepage: http://www.bmschmidtlab.de
Supporting information for this article is given via a link at the end of the document.
Abstract: To create innovative materials, efficient control and
behaviour of POCs.[10b,11] Recently, we were able to demonstrate
the beneficial effect of fluorine substitution towards gas
engineering of pore sizes and their characteristics, crystallinity and
4
6
[13]
stability is required. Eight hybrid Tri Di imine cages with a tuneable
adsorption of POCs. We investigate the synthesis of hybrid-
4
6
degree of fluorination and one fully fluorinated Tri Di imine cage are
investigated. Although the fluorinated and the non-fluorinated building
blocks used herein differ vastly in reactivity, we are able to gain control
over the outcome of the self-assembly process, by carefully
controlling the feed ratio. This represents the first hybrid material
based on fluorinated/hydrogenated porous organic cages (POCs).
These cages with unlimited miscibility in the solid state were obtained
as highly crystalline samples after recrystallization and even showed
retention of the crystal lattice, forming alloys. All mixtures and the fully
POCs containing non-fluorinated and fluorinated building blocks,
resulting in a complex dynamic material library. We examine the
different reactivities of the two isostructural ditopic aldehydes[
and their influence on the outcome of dynamic Tri Di6 imine
condensations. The effect of fluorine substitution on the thermal
stability and crystallinity of these novel hybrid materials is
analysed to evaluate the result of our library approach. In the high-
throughput study of Cooper and co-workers, the formation of a
8j]
4
4
6
Tri Di imine cage by reaction of four 1,3,5-tris(2-aminomethyl)-
2,4,6-triethyl-benzene (A) units with six terephthalaldehyde
molecules (TA) was reported.[9d] We chose this motif to
subsequently exchange the six non-fluorinated TA building blocks
for tetrafluoroterephthalaldehyde (TFTA), allowing us to precisely
monitor the influence of fluorinated subunits in relation to cage
properties (solid state self-assembly and thermal stability). The
large difference in electron density and overall quadrupolar
moment is envisioned to have a significant effect on the cavity of
the resulting imine cages. We present a series of eight partially
4
6
fluorinated Tri Di imine cage were analysed by MALDI-MS, SCXRD,
PXRD and in regards to thermal stability (TGA).
Nature efficiently uses the principles of non-covalent self-
assembly together with self-sorting phenomena to generate
complex, functional architectures from several different and often
complex building blocks bearing function. In an abiological
context, the design of porous materials, suitable for gas
adsorption applications, requires precise control over the interior
and exterior pore size, accessibility and the stability of the material
itself.[1] A large range of materials, containing a high amount of
fluorine atoms, have in the past been attributed with increased
thermal stability, higher crystallinity and higher gas uptake
compared to their non-fluorinated counterparts.[ The group of
Miljanić was able to capture fluorinated anaesthetics inside a
porous crystal, consisting of extensively fluorinated aromatic
molecules.[6a,b] The beneficial effect of fluorine substitution does
even further extend to increased crystallinity, not only in the
crystal lattice of small molecules, but also in COFs.[5,7] Dynamic
covalent bond formation, often employing amine and aldehyde
building blocks for self-correcting imine formation, generates
dynamic cage-type compounds with various properties up to
complex multicomponent libraries.[8] Porous organic cages
4
6
fluorinated imine cages, as well as a fully fluorinated Tri Di imine
cage using building blocks with a large difference in reactivity for
the first time.
2-5]
(
POCs), as an emerging class of porous materials, have been
extensively studied throughout the last decade.[
9a,c,10e-g]
Significant contributions include control of pore size,[
9b,e,10b]
cage
and pore geometry,[9f] guest binding behaviour[10g] and
engineering of the overall crystal packing,[9f,10f] demonstrating a
great degree of control over the material properties.[9,10] Only few
articles focus on the role of fluorine in dynamic imine chemistry
and as the possibility to influence porosity and guest-binding
Figure 1. Synthetic scheme of the reaction of amine A with TA and fluorinated
TFTA, in different feed ratios, targeting the hybrid cages
4 X
A H F(6-X); the
hexagons indicate the corresponding compositions of the hybrid cages
throughout the manuscript.
1
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.202100891
COMMUNICATION
Previous studies utilized chiral self-sorting[10c] or structurally
accompanied by precipitation of the product from the reaction
solvent. In those cases, the time until precipitation occurs, can
serve as an indicator for reactivity. To study these differences,
chloroform was chosen as solvent. In our experience, possible
oligomeric side products are solubilized efficiently in chloroform,
facilitating error correction of dynamic imine condensation
different building blocks to desymmetrize POCs by imine
condensation to create amorphous materials.[
14]
Along with
increasing disorder within the material, this approach allows us to
generate a crystalline supramolecular alloy after recrystallisation
of the hybrid cage mixtures, freely composed of highly fluorinated
and non-fluorinated POCs.[
15]
4 6 4 5 1
reactions. Under these given conditions, pure A H and A H F
Five equivalents of amine A (slight excess) were reacted with
varying ratios of TA and TFTA at room temperature in either
methanol or chloroform with an amine concentration of 4 mmol/L.
As a systematic nomenclature for these mixed cages we use
mixtures start to precipitate after 24 h, whereas all cage mixtures
with a TFTA count >1 start precipitating almost immediately (as
indicated by NMR experiments, Figure S1-S2). This underlines
the anticipated high reactivity of the TFTA molecules and hence,
shorter reaction times. But one has to consider, that TFTA
containing cage products are also often less soluble in
comparison to non-fluorinated congeners, from our observations.
To further investigate the different reactivities, we conducted
kinetic NMR experiments and DFT calculations (Figure S1-S4
and S17). The two approaches to generate essentially all
4 X
A H F(6-X) herein, where X is the number of incorporated TA
molecules and the number following the letter F represents the
number of TFTA moieties per cage molecule (Figure 1). After a
period of 2 days, we could isolate a colourless solid directly from
the reaction mixture by filtration. Analysis by H, 19F NMR and
DOSY experiments after redissolving the solids revealed the
successful synthesis of a narrow distribution of hybrid cage
species around the targeted composition. All cage compounds
1
4 X 4 6 4 6
A H F(6-X) species are: a) by mixing the pure A F and A H cages
in the corresponding ratios to generate a distribution of mixed
cage compounds in hot chloroform over prolonged time (Figure
S6-S7) or b), by mixing TFTA and TA with the amine A in ratios
4 X
within the mixture following the composition A H F(6-X), are
expected to be of similar size and indeed show comparable
diffusion coefficients around D = 4.5*10-10 m s corresponding to
2
-1
4 X
corresponding to the targeted A H F(6-X) composition. The latter
a solvodynamic radius of 0.90 nm in solution (Table S1). A
approach is clearly faster since the reaction times are only 2-3
days instead of several weeks needed for the former system to
reach its equilibrium state.
4 5 1 4 4 2
statistical distribution of the mixed cages A H F , A H F and
A
4
H
3
F
3
alongside A is also confirmed by MALDI-MS analysis
4 6
H
of the precipitate (Figures S59-S68). According to the general
procedure, to our delight, all anticipated hybrid cage mixtures with
varying fluorine content can be accessed and were characterized
as obtained from the reaction mixture comprehensively by using
MALDI-MS, NMR and powder XRD (Figure S39 and S46-S68).
Directly corresponding to the feed ratio of TA and TFTA, a narrow
gaussian-like distribution around the targeted composition
demonstrates very good control over the outcome of the cage
formation even after recrystallization (Figure 2).
Immediately after mixing, the consumption of TFTA can be
observed. Fast formation of precipitate (potentially oligomeric
species with high fluorine content) can be noted, without new
imine signals in 1H NMR being observed. TFTA is consumed
completely, before the majority of TA reacted. The oligomeric
species containing TFTA appear to act as a reservoir and are not
removed from the system completely (Figure S1-S2).
Redissolved fragments react then with the less reactive TA
building blocks in a dynamic equilibrium, resulting in the observed
mixtures, an important addition to the recent investigation on
hydrogenated and deuterated POCs.[16]
As anticipated, the decomposition temperatures are increasing
with higher fluorine content. The onset temperature of A
4 6
H ,
2
66 °C could be increased to 313 °C for A . Each subsequent
4 6
F
substitution of TA versus TFTA increases the decomposition
onset by roughly 5 °C (Figure 3e). This is in perfect agreement
with the influence of fluorine substitution on porous organic
materials.[ We were able to obtain single-crystals (Figure 3a) of
all targeted imine cage compounds and obtained structural data
2d]
4 6 4 1 5 4 2 4 4 4 2
for pure A F and A H F , A H F , A H F
alloys.[17] The hybrid
cages crystallize in regular rhombohedral shapes (Figure 3c). To
our surprise, the single-crystals also did not consist of one cage
isomer but exhibited the same gaussian distribution of hybrid
cages, within the crystal lattice (Figure S61-S67). All hybrid cage
alloys crystallize in the highly symmetric rhombohedral space
group R-3, with one whole and a third molecule A and two para-
substituted building blocks in the asymmetric unit. Due to their
large size and voids containing ordered and disordered solvent
molecules within the lattice, refinement was carried out as
described for each crystal (Page S29 ff.). The TFTA and TA
motifs can be exchanged freely in the crystal lattice at the two
available, crystallographically independent positions and are
furthermore moved by the representative symmetry operations.
The average fluorine content was estimated from the diffraction
data and compared to MALDI-MS data of the single-crystals,
Figure 2. MALDI-MS spectra of the recrystallized cage alloys a) A
4 6 4 1 5
F , b) A H F ,
c) A , d) A , e) A and mixture f) A obtained using different
4
H
F
2 4
4
H
F
3 3
4
H
F
4 2
4 5 1
H F
feed ratios of TA and TFTA with 5 equivalents of amine A, inlays each indicate
the targeted composition. Using a slight excess of amine A, yields are
significantly improved.[9d] For the MALDI-MS spectra of all mixtures isolated
directly from the reaction by either filtration or evaporation of the solvent at
ambient temperatures, see Figures S59-S68.
Considering TFTA bears four highly electronegative substituents,
we were intrigued to examine the differences in reactivity
compared to TA, since the synthesis of imine cages is often
2
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.202100891
COMMUNICATION
Figure 3. a) Structure of A
and wR = 0.3157, the fluorine content is estimated to be 48 percent for both crystallographically unequal fluorobenzenes within the structure (the variance is the
highest for A
structures for A
4 2 4 1
H F obtained from SXRD data; the structure was measured at 100 K and solved in the rhombohedral R-3 with RInt = 0.1182, R = 0.0931
2
4
H
2
F
4
because of a low resolution and framework disorder, see the Supporting Information); solvents are omitted for clarity; b) overlay of the crystal
(blue), A (pink) and A (orange); c) microscopic photographs taken of single-crystals before XRD measurements (approx. 0.2-0.3 mm);
4
F
6
4
H
1
F
5
4 2 4
H F
d) solvent accessible surface area without solvents for a molecular probe with 1.2 Å radius (outer surface area = blue, inner surface = orange) within the crystal
lattice; e) thermogravimetric analyses of all hybrid cage mixtures; the dotted lines indicate the onset temperature of decomposition (Table S2).
showing excellent agreement. In the solid state, two adjacent
cages pack window-to window generating a pore of roughly 18 Å
length, as depicted (Figure 3d). Close π-π-stacking in a distance
of about 3.5 Å connects neighbouring cages, whereas stacking
with former amine building block A is hampered by the bulky ethyl
groups, leading to centroid-to-centroid distances of around 4.5 Å.
These results suggest a) the influence of fluorinated building
blocks on the crystallinity, as only the non-fluorinated imine cage
could not be crystallized and b) an interchangeability of TFTA and
the future and marks an entry point for fluorinated organic cages
into the field of supramolecular materials chemistry. Our study is
an important addition to the dynamic covalent chemistry of
complex POCs, employing three or more building blocks and lays
the foundation for further research regarding exciting properties
of this new class of organic cages.
Acknowledgements
[
18]
TA both in the parent cage (multivariate) and in the crystal
4
6
lattice of these Tri Di imine cages (Figure 3b), making them
indeed tuneable supramolecular alloy materials in the solid state.
We thank Dr. Markus Leutzsch of the MPI for Coal Research for
help with the NMR measurements and Dr. Raphael Wiedey and
Prof. Dr. Peter Kleinebudde for access to a powder X-ray
diffractometer. This work was supported by the Fonds der
Chemischen Industrie by a Kekulé Fellowship (T.K.) by the North
Rhine-Westphalian Academy of Sciences, Humanities and the
Arts (B.M.S.) and funded by the Deutsche Forschungs-
gemeinschaft (DFG, German Research Foundation) – SCHM
4 2 4
For the crystal of A H F , this would essentially result in a
septenary crystal not counting isomers, which would even imply a
denary cocrystal (see Figure 2c).
We successfully synthesized and characterized a family of
4
6
dynamic Tri Di imine cages,
4 X (6-X)
A H F , containing highly
fluorinated building blocks. To the best of our knowledge, this is
the first report of a true multivariate crystalline supramolecular
alloy based on POCs.[19] The introduction of electron-deficient and
therefore highly reactive aldehydes in any given ratio increases
the stability and crystallinity of the obtained material in a step-wise
3101/5-1.
Keywords: fluorine chemistry • cage compounds • dynamic
fashion, without influencing the overall crystal packing.
formation study using different feed ratios suggests a faster
reaction of fluorinated aldehydes in comparison to the non-
fluorinated counterparts, where imine cage A H is formed slower.
4 6
The fine tuning of the cavity of an organic cage will enable precise
control over the selectivity of the resulting solid state materials in
A
covalent chemistry • crystal structures • materials
References
[1]
a) A. G. Slater, A. I. Cooper, Science 2015, 348, aaa8075; b) T. Hasell,
A. I. Cooper, Nat. Rev. Mat. 2016, 1, 16053.
3
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.202100891
COMMUNICATION
[2]
a) A. Cadiau, Y. Belmabkhout, K. Adil, P. M. Bhatt, R. S. Pillai, A.
M. A. Little, V. Santolini, C. D. Jones, R. Evans, C. Wilson, X. Wu, M. F.
Thorne, M. J. Bennison, P. Cui, A. I. Cooper, K. E. Jelfs, A. G. Slater,
Angew. Chem. Int. Ed. 2020, 59, 16755-16763; Angew. Chem. 2020, 132,
16898-16906; c) M. Liu, L. Zhang, M. A. Little, V. Kapil, M. Ceriotti, S.
Yang, L. Ding, D. L. Holden, R. Balderas-Xicohténcatl, D. He, R. Clowes,
S. Y. Chong, G. Schütz, L. Chen, M. Hirscher, A. I. Cooper, Science 2019,
366, 613-620; d) R. L. Greenaway, V. Santolini, M. J. Bennison, B. M.
Alston, C. J. Pugh, M. A. Little, M. Miklitz, E. G. B. Eden-Rump, R.
Clowes, A. Shakil, H. J. Cuthbertson, H. Armstrong, M. E. Briggs, K. E.
Jelfs, A. I. Cooper, Nat. Commun. 2018, 9, 2849; e) S. Jiang, Y. Du, M.
Marcello, E. W. Corcoran Jr, D. C. Calabro, S. Y. Chong, L. Chen, R.
Clowes, T. Hasell, A. I. Cooper, Angew. Chem. Int. Ed. 2018, 57, 11228-
11232; Angew. Chem. 2018, 130, 11398-11402; f) M. J. Bojdys, M. E.
Briggs, J. T. A. Jones, D. J. Adams, S. Y. Chong, M. Schmidtmann, A. I.
Cooper, J. Am. Chem. Soc. 2011, 133, 16566-16571.
Shkurenko, C. Martineau-Corcos, G. Maurin, M. Eddaoudi, Science 2017,
356, 731-735; b) T.-H. Chen, I. Popov, O. Zenasni, O. Daugulis, O. Š.
Miljanić, Chem. Commun. 2013, 49, 6846-6848; c) P. Pachfule, Y. Chen,
J. Jiang, R. Banerjee, Chem. Eur. J. 2012, 18, 688-694; a recent review:
d) Z. Zhang, O. Š. Miljanić, Org. Mat. 2019, 1, 19-29.
[3]
a) C. Yang, X. Wang, M. A. Omary, J. Am. Chem. Soc. 2007, 129, 15454-
15455; b) C. Yang, U. Kaipa, Q. Z. Mather, X. Wang, V. Nesterov, A. F.
Venero, M. A. Omary, J. Am. Chem. Soc. 2011, 133, 18094-18097; for
recent reviews on fluorinated MOFs, see: c) K. Jayaramulu, F. Geyer, A.
Schneemann, Š. Kment, M. Otyepka, R. Zboril, D. Vollmer, R. A. Fischer,
Adv. Mater. 2019, 31, 1900820; d) S.-I. Noro, T. Nakamura, NPG Asia
Materials, 2017, 9, e433.
[
4]
5]
a) P. M. Bhatt, Y. Belmabkhout, A. Cadiau, K. Adil, O. Shekhah, A.
Shkurenko, L. J. Barbour, M. Eddaoudi, J. Am. Chem. Soc. 2016, 138,
9
301-9307; b) T.-H. Chen, I. Popov, W. Kaveevivitchai, Y.-C. Chuang,
Y.-S. Chen, A. J. Jacobson, O. Š. Miljanić, Angew. Chem. Int. Ed. 2015,
4, 13902-13906; Angew. Chem. 2015, 127, 14108-14112.
[10] a) J. C. Lauer, W.-S. Zhang, F. Rominger, R. R. Schröder, M. Mastalerz,
Chem. Eur. J. 2018, 24, 1816-1820; b) S. M. Elbert, N. I. Regenauer, D.
Schindler, W. S. Zhang, F. Rominger, R. R. Schröder, M. Mastalerz,
Chem. Eur. J. 2018, 24, 11438-11443; c) D. Beaudoin, F. Rominger, M.
Mastalerz, Angew. Chem. Int. Ed. 2017, 56, 1244-1248; Angew. Chem.
2017, 129, 1264-1268; d) M. W. Schneider, I. M. Oppel, A. Griffin, M.
Mastalerz, Angew. Chem. Int. Ed. 2013, 52, 3611-3615; Angew. Chem.
2013, 125, 3699-3704; e) M. W. Schneider, I. M. Oppel, M. Mastalerz,
Chem. Eur. J. 2012, 18, 4156-4160; for reviews about the topic see also:
f) M. Mastalerz, Acc. Chem. Res. 2018, 51, 2411-2422; g) M. Mastalerz,
Angew. Chem. Int. Ed. 2010, 49, 5042-5053; Angew. Chem. 2010, 122,
5164-5175.
5
[
a) A. Comotti, F. Castiglioni, S. Bracco, J. Perego, A. Pedrini, M. Negroni,
P. Sozzani, Chem. Commun. 2019, 55, 8999-9002; b) G. Wang, K. Leus,
H. S. Jena, C. Krishnaraj, S. Zhao, H. Depauw, N. Tahir, Y.-Y. Liu, P.
Van Der Voort, J. Mat. Chem. A, 2018, 6, 6370-6375; c) S. B. Alahakoon,
G. T. McCandless, A. A. K. Karunathilake, C. M. Thompson, R. A.
Smaldone, Chem. Eur. J. 2017, 23, 4255-4259.
[
6]
7]
a) T.-H. Chen, I. Popov, W. Kaveevivitchai, Y.-C. Chuang, Y.-S. Chen,
O. Daugulis, A. J. Jacobson, O. Š. Miljanić, Nat. Commun. 2014, 5, 5131;
b) Z. Yang, S. Wang, Z. Zhang, W. Guo, K. Jie, M. I. Hashim, O. Š.
Miljanić, D.-E. Jiang, I. Popovs, S. Dai, J. Mat. Chem. A, 2019, 7, 17277-
[11] a) T. Jiao, L. Chen, D. Yang, X. Li, G. Wu, P. Zeng, A. Zhou, Q. Yin, Y.
Pan, B. Wu, X. Hong, X. Kong, V. M. Lynch, J. L. Sessler, H. Li, Angew.
Chem. Int. Ed. 2017, 56, 14545-14550; Angew. Chem. 2017, 129,
14737-1474; b) T. Kunde, T. Pausch, G. R. Reiss, B. M. Schmidt, Synlett
2021, DOI: 10.1055/a-1470-6050.
17282. c) T.-H. Chen, W. Kaveevivitchai, A. J. Jacobson, O. Š. Miljanić,
Chem. Commun. 2015, 51, 14096-14098.
[
a) M. I. Hashim, H. T. M. Le, T.-H. Chen, Y.-S. Chen, O. Daugulis, C.-W.
Hsu, A. J. Jacobson, W. Kaveevivitchai, X. Liang, T. Makarenko, O. Š.
Miljanić, I. Popovs, H. V. Tran, X. Wang, C.-H. Wu, J. I. Wu, J. Am. Chem.
Soc. 2018, 140, 6014-6026; b) J.-H. Dou, Y.-Q. Zheng, Z.-F. Yao, Z.-A.
Yu, T. Lei, X. Shen, X.-Y. Luo, J. Sun, S.-D. Zhang, Y.-F. Ding, G. Han,
Y. Yi, J.-Y. Wang, J. Pei, J. Am. Chem. Soc. 2015, 137, 15947-15956; c)
K. Reichenbächer, H. I. Süss, J. Hulliger, Chem. Soc. Rev. 2005, 34, 22-
[12] a) Q. Liao, C. Ke, X. Huang, G. Zhang, Q. Zhang, Z. Zhang, Y. Zhang,
Y. Liu, F. Ning, K. Xi, J. Mat. Chem. A, 2019, 7, 18959-18970; b) B. M.
Schmidt, A. K. Meyer, D. Lentz, CrystEngComm. 2017, 19, 1328-1333.
[13] T. Kunde, E. Nieland, H. V. Schröder, C. A. Schalley, B. M. Schmidt,
Chem. Commun. 2020, 56, 4761-4764.
3
0.
[14] S. Jiang, J. T. A. Jones, T. Hasell, C. E. Blythe, D. J. Adams, A. Trewin,
A. I. Cooper, Nat. Commun. 2011, 2, 207.
[8]
a) A. W. Markwell-Heys, M. L. Schneider, J. M. L. Madridejos, G. F.
Metha, W. M. Bloch, Chem. Commun. 2021, 57, 2915-2918; b) R. A. S.
Vasdev, J. A. Findlay, D. R. Turner, J. D. Crowley, Chem. Asian J. 2021,
[15] A. Simonov, A. L. Goodwin, Nat. Rev. Chem. 2020, 4, 657-673.
[16] T. H. Schick, F. Rominger, M. Mastalerz, J. Org. Chem. 2020, 85, 13757-
13771.
16, 39-43; c) L. S. Lisboa, J. A. Findlay, L. J. Wright, C. G. Hartinger, J.
D. Crowley, Angew. Chem. Int. Ed. 2020, 59, 11101-11107; Angew.
Chem. 2020, 132, 11194-11200; d) M. L. Schneider, O. M. Linder-Patton,
W. M. Bloch, Chem. Commun. 2020, 56, 12969-12972; e) D. Preston, A.
R. Inglis, J. D. Crowley, P. E. Kruger, Chem. Asian J. 2019, 14, 3404-
[17] Deposition numbers 2047255 (for A
4 6 4 1 5
F ), 2047256 (A H F ) and 2047257
(A ) contain the supplementary crystallographic data for this paper.
4 2 4
H F
These data are provided free of charge by the joint Cambridge
Crystallographic Data Centre and Fachinformationszentrum Karlsruhe.
[18] H. Deng, C. J. Doonan, H. Furukawa, R. B. Ferreira, J. Towne, C. B.
Knobler, B. Wang, O. M. Yaghi, Science 2010, 327, 846-850.
3408; f) S. Klotzbach, F. Beuerle, Angew. Chem. Int. Ed. 2015, 54,
0356-10360; Angew. Chem. 2015, 127, 10497-10502; g) A. Dhara, F.
1
Beuerle, Chem. Eur. J. 2015, 21, 17391-17396; h) Kołodziejski, A. R.
Stefankiewicz, J.-M. Lehn, Chem. Sci. 2019, 10,1836-1843; for a review
see: i) F. Beuerle, B. Gole, Angew. Chem. Int. Ed. 2018, 57, 4850-4878;
Angew. Chem. 2018, 130, 4942-4972; for nomenclature based on the
topicity of the precursors as used herein, see j) V. Santolini, M. Miklitz, E.
Berardo, K. E. Jelfs, Nanoscale 2017, 9, 5280-5298.
[19] a) A. G. Slater, M. A. Little, A. Pulido, S. Y. Chong, D. Holden, L. Chen,
C. Morgan, X. Wu, G. Cheng, R. Clowes, M. E. Briggs, T. Hasell, K. E.
Jelfs, G. M. Day, A. I. Cooper, Nat. Chem. 2017, 9, 17-25; b) M. A. Little,
M. E. Briggs, J. T. A. Jones, M. Schmidtmann, T. Hasell, S. Y. Chong, K.
E. Jelfs, L. Chen, A. I. Cooper, Nat. Chem. 2015, 7, 153-159; c) T. Hasell,
S. Y. Chong, M. Schmidtmann, D. J. Adams, A. I. Cooper, Angew. Chem.
Int. Ed. 2012, 51, 7154-7157; Angew. Chem. 2012, 124; 7266-7269.
[9]
a) T. Tozawa, J. T. A. Jones, S. I. Swamy, S. Jiang, D. J. Adams, S.
Shakespeare, R. Clowes, D. Bradshaw, T. Hasell, S. Y. Chong, C. Tang,
S. Thompson, J. Parker, A. Trewin, J. Bacsa, A. M. Z. Slawin, A. Steiner,
A. I. Cooper, Nat. Mater. 2009, 8, 973-978; b) V. Abet, F. T. Szczypiński,
4
This article is protected by copyright. All rights reserved.

Chemistry - A European Journal
10.1002/chem.202100891
COMMUNICATION
Entry for the Table of Contents
A supramolecular alloy, freely composed of eight hybrid Tri Di6
imine cages with a tuneable degree of fluorination can be created
with high crystallinity. Although the fluorinated and the non-
fluorinated building blocks used herein differ vastly in reactivity,
gaining control over the outcome of the self-assembly process
was achieved by carefully controlling the feed ratio.
4
Institute and/or researcher Twitter usernames: @BmSchmidtlab,
@HHU_de
5
This article is protected by copyright. All rights reserved.