The Synthesis of Organic Molecules of Intrinsic Microporosity Designed to Frustrate Efficient Molecular Packing

Article abstract of DOI:10.1002/chem.201504212

Efficient reactions between fluorine-functionalised biphenyl and terphenyl derivatives with catechol-functionalised terminal groups provide a route to large, discrete organic molecules of intrinsic microporosity (OMIMs) that provide porous solids solely by their inefficient packing. By altering the size and substituent bulk of the terminal groups, a number of soluble compounds with apparent BET surface areas in excess of 600m² g^-1 are produced. The efficiency of OMIM structural units for generating microporosity is in the order: propellane>triptycene>hexaphenylbenzene>spirobifluorene>naphthyl=phenyl. The introduction of bulky hydrocarbon substituents significantly enhances microporosity by further reducing packing efficiency. These results are consistent with findings from previously reported packing simulation studies. The introduction of methyl groups at the bridgehead position of triptycene units reduces intrinsic microporosity. This is presumably due to their internal position within the OMIM structure so that they occupy space, but unlike peripheral substituents they do not contribute to the generation of free volume by inefficient packing.

Full text of DOI:10.1002/chem.201504212

DOI: 10.1002/chem.201504212
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Microporous Materials |Hot Paper|
The Synthesis of Organic Molecules of Intrinsic Microporosity
Designed to Frustrate Efficient Molecular Packing
Rupert G. D. Taylor,[b] C. Grazia Bezzu,[a] Mariolino Carta,[a] Kadhum J. Msayib,[a]
Jonathan Walker,[b] Rhys Short,[b] Benson M. Kariuki,[b] and Neil B. McKeown*[a]
Abstract: Efficient reactions between fluorine-functionalised
biphenyl and terphenyl derivatives with catechol-functional-
ised terminal groups provide a route to large, discrete or-
ganic molecules of intrinsic microporosity (OMIMs) that pro-
vide porous solids solely by their inefficient packing. By al-
tering the size and substituent bulk of the terminal groups,
a number of soluble compounds with apparent BET surface
areas in excess of 600 m2 gÀ1 are produced. The efficiency of
OMIM structural units for generating microporosity is in the
order: propellane>triptycene>hexaphenylbenzene>spiro-
bifluorene>naphthyl=phenyl. The introduction of bulky hy-
drocarbon substituents significantly enhances microporosity
by further reducing packing efficiency. These results are con-
sistent with findings from previously reported packing simu-
lation studies. The introduction of methyl groups at the
bridgehead position of triptycene units reduces intrinsic mi-
croporosity. This is presumably due to their internal position
within the OMIM structure so that they occupy space, but
unlike peripheral substituents they do not contribute to the
generation of free volume by inefficient packing.
Introduction
pack together efficiently in the solid state, as demonstrated by
the polymers of intrinsic microporosity (PIMs).[3b,12,13] Ordered
porous molecular materials may be obtained from the self-as-
sembly of the component molecules into a crystalline porous
packing arrangement,[9,14] or from the crystallisation of molecu-
lar cages, which act as prefabricated pores. For example, the
groups of Cooper and Mastalerz have demonstrated that mo-
lecular cages, produced from multiple Schiff base condensa-
tions between simple amine and aldehyde precursors, can pro-
There is increasing interest in the study of microporous materi-
als made using organic components,[1] driven by potential ap-
plications in gas storage,[2] selective gas separation mem-
branes,[3] heterogeneous catalysis,[4] and nanoparticle encapsu-
lation.[5] Broadly, microporous materials can be subdivided into
two structural classes: ordered materials, the porosity of which
typically arises from their crystalline structure (for example,
zeolites,[6] metal–organic frameworks (MOFs),[4a,7] covalent or-
ganic frameworks (COFs),[8] and porous molecular crystals[9]),
and amorphous materials, the porosity of which arises from
a disordered framework (for example, activated carbons,[10] hy-
percrosslinked polymers,[11] and other porous polymer net-
works[12]). The majority of both ordered and amorphous micro-
porous materials are based on network structures, which are
inherently insoluble. However, demand for solution-process-
able porous materials has led to interest in non-network poly-
meric and molecular materials. For example, microporosity can
be generated from the inability of soluble polymer chains to
duce soluble materials with apparent BET surface areas (SABET
)
approaching 1400 m2 gÀ1.[15] Recently, Mastalerz et al. have cre-
ated highly porous cages from triptycene-based precursors
that were suitably functionalised to undergo Schiff base con-
densations[16] or boronic ester formation.[17] Using the latter,
a crystalline molecular material with a SABET of 3758 m2 gÀ1 was
produced. The prefabricated pore structure of macrocycles[18]
and cages[15c,h,19] can also generate microporosity from amor-
phous packing in the solid state. However, amorphous micro-
porous materials derived from discrete organic molecules that
are neither cages nor macrocycles are still relatively rare.[20]
We are engaged in a joint modelling[21] and synthesis[20b] pro-
gramme to investigate organic molecules of intrinsic micro-
porosity (OMIMs), which we define as discrete molecular com-
pounds that are designed to generate microporous materials
solely from their inability to pack efficiently in the solid state.
Theory suggests that for both two-[22] and three-dimensional[23]
objects, the most inefficient packing is produced when the
constituent shapes possess highly concave faces. Accordingly,
our design strategy is to combine rigid, aromatic precursors
(Figure 1) to form large molecules with multiple concavities
(Figure 2). Precursors are composed of core units (1, 2) that
possess ortho-difluorine functionality and terminal units (3-9)
[a] Dr. C. G. Bezzu, Dr. M. Carta, Dr. K. J. Msayib, Prof. N. B. McKeown
EaStCHEM School of Chemistry, University of Edinburgh
David Brewster Road, Edinburgh, EH9 3FJ (UK)
E-mail: neil.mckeown@ed.ac.uk
[b] Dr. R. G. D. Taylor, Dr. J. Walker, Dr. R. Short, Dr. B. M. Kariuki
School of Chemistry, Cardiff University
Cardiff, CF10 3AT (UK)
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/chem.201504212.
ꢀ 2015 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA.
This is an open access article under the terms of the Creative Commons At-
tribution License, which permits use, distribution and reproduction in any
medium, provided the original work is properly cited.
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Figure 1. Precursors 1–9 (top) and general reaction scheme (box) for reaction of catechol terminal units with fluorinated cores 1 (left) and 2 (right).
with catechol functionality, allowing for efficient combination
by a double nucleophilic aromatic substitution to give dioxan
fused units, a reaction previously utilised successfully in
the synthesis of PIMs.[13,24] We selected 4,4’-dicyano-
2,2’,3,3’,5,5’,6,6’-octafluorobiphenyl (1)[25] as an OMIM core
owing to the two electron-withdrawing nitrile groups, en-
couraging efficient dioxan formation. By serendipity,
2,2’,2’’,3,3’’,5,5’,5’’,6,6’,6’’-undecafluoro-[1,1’:3’,1’’-terphenyl]-
4,4’,4’’-tricarbonitrile (2) was obtained as a by-product during
the synthesis of 1, and was investigated owing to its higher re-
active functionality, allowing access to highly substituted mate-
rials. Catechol (3)- and naphthalene (4)-based arms were se-
lected as base-line controls to examine the effect of increasing
arm length and adding substituents. Triptycene (5 and 6)[26,27]
and bulkier arm groups, based on spirobifluorene (7),[28] pro-
pellane (8),[29] and hexaphenylbenzene (9),[30] were selected
owing to their high internal free volume[26b] and proven porosi-
ty-enhancing properties in PIMs and other microporous poly-
mers.
mediated coupling of pentafluorobenzonitrile by adapting
a procedure described in a patent.[25] The terphenyl core pre-
cursor 2 was isolated as an unexpected by-product in low
yield (6%) but in sufficient quantity to facilitate its use as
a core for adduct synthesis. Each adduct was prepared by
mixing the core precursor 1 or 2 with an excess of an arm unit
chosen from 3–9 (Figure 1) in anhydrous DMF at 658C for 48 h
in the presence of potassium carbonate. Each adduct
(Figure 2) was purified either by column chromatography or by
repeated trituration to remove more soluble impurities. Owing
to the lack of symmetry of many of the substituted precursors,
several of the reported OMIMs/adducts were isolated as mix-
tures of inseparable regioisomers (Table 1). The molecular
mass, homogeneity and discrete nature of each adduct was
confirmed by matrix-assisted laser desorption ionisation mass
spectrometry (MALDI-MS) and gel permeation chromatography
(GPC). For each adduct, the polydispersity index obtained from
GPC was less than 1.1.
The potential of 1 and 2 as OMIM cores was first tested by
their reaction with excess 3a to ascertain their reactivity to-
wards aromatic nucleophilic substitution. After purification,
crystals of the resultant adducts (10 and 14) were achieved by
slow diffusion of methanol into chloroform solutions. X-ray
crystallography coupled with 19F NMR spectroscopy (Figure 3)
revealed these adducts to be the tetra-substituted adduct (10),
with a near orthogonal relationship between the two long
Results and Discussion
Synthesis
The biphenyl fluorinated core precursor 1 was prepared in
moderate yield (34%) by the hexaethylphosphorous triamide
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Figure 2. Structures of compounds 10–39, including OMIM-1 to OMIM-18.
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Table 1. OMIM/adduct data for compounds 10–39.
Compound
number
OMIM
number[a]
Precursors
Apparent BET
Pore volume
Yield
[%]
Isomerically
pure (Y/N)
CCDC
number
surface area
[cm3 gÀ1
]
[b]
[m2 gÀ1
]
10[c]
11[c]
12[c]
13
14
15
–
–
–
–
–
–
–
–
–
–
–
–
1+3a
1+3b
1+3c
1+3d
2+3a
2+3b
2+3c
1+4a
1+4b
1+4c
2+4a
2+4b
2+4c
1+5a
1+5b
1+5c
1+5d
1+5e
2+5a
2+5b
2+5c
2+5d
2+5e
1+6
7
41
67
51
13
7
102
25
260
132
29
259
347
485
462
654
599
702
423
351
726
651
698
622
333
595
407
591
471
612
0.03
0.15
0.23
0.13
0.05
0.01
0.37
0.05
0.33
0.25
0.11
0.35
0.41
0.40
0.33
0.54
0.42
0.60
0.44
0.30
0.72
0.47
0.44
0.64
0.28
0.45
0.46
0.49
0.36
0.49
74
80
70
90
87
64
88
44
64
39
13
43
97
73
51
91
47
83
30
79
81
65
77
86
90
56
73
78
88
84
Y
1406071
N
N
Y
–
–
–
Y
1406073
N
N
Y
N
N
Y
N
N
Y
–
–
16
17[c]
18[c]
19[c]
20
1406072
–
–
–
–
21
22
OMIM-7
OMIM-1
OMIM-8
OMIM-4
OMIM-9
OMIM-5
OMIM-10
OMIM-11
OMIM-12
OMIM-13
OMIM-14
OMIM-6
OMIM-2
OMIM-3
OMIM-15
OMIM-16
OMIM-17
OMIM-18
–
23[c,d,e]
24
955894
1406070
Y
25[d,e]
26
N
N
Y
Y
Y
N
N
Y
N
N
N
N
N
N
N
–
–
27[e]
28
973327
–
–
–
–
–
–
–
–
–
–
–
–
29
30
31
32
33[e]
34[d]
35[d]
36
37
38
1+7
1+8
1+9
2+6
2+7
2+8
39
[a] We only classify those materials with an apparent BET surface area of more than 300 m2 gÀ1 as OMIMs. [b] Measured experimentally at 77 K following de-
gassing at 1358C under vacuum for 15 h. [c] Structure previously reported for packing simulation.[21b] [d] Structure previously reported for packing simula-
tion.[21a,c] [e] Structure and experimental data previously reported.[20b]
struts of the molecule, and the penta-substituted adduct (14),
with one residual fluorine atom on the central aryl ring. This
substitution pattern was found consistently with all catechol
adducts of 1 and 2 in this study. Bridged products, in which
a single arm bridges two cores (Supporting Information, Fig-
ure S1) were often found as trace impurities; however, these
were readily removed by column chromatography. Detailed
synthetic procedures and spectroscopic data for all novel pre-
cursors and adducts are given in the Supporting Information.
dichloromethane and THF), which combined with the in-
creased porosity, suggests a disruption of the cohesive interac-
tions between the constituent molecules. To further study this
effect, 2,3-dihydroxy-5,5,8,8-tetramethyl-6,6,7,7-tetrahydronap-
thalene (3d) was prepared and combined with 1 to give 13,
which demonstrates comparable properties to 12. Simple ad-
ducts of core 2 were also prepared using three catechol pre-
cursors 3a–c. Much like its biphenyl analogue, terphenyl-based
adduct 14 was poorly soluble in common solvents and pos-
sesses a negligible apparent SABET of 13 m2 gÀ1. However, the
addition of two tert-butyl groups per arm gave a highly soluble
material (16) with a greater apparent SABET of 102 m2 gÀ1 over
its biphenyl analogue (12, 67 m2 gÀ1), suggesting that the
higher functionality of the terphenyl core generates a more
porous material.
Discussion
The simplest adduct (10) was found to be effectively non-mi-
croporous, with an apparent BET surface area (SABET) of
7 m2 gÀ1 as measured by nitrogen sorption at 77 K and it was
highly insoluble, suggesting that the constituent molecules are
able to pack together in an efficient manner, despite its awk-
ward displaced cruciform structure. As predicted by molecular
modelling,[21b] the introduction of bulky tert-butyl groups to
the periphery of the adducts (11, 12) improved apparent mi-
croporosity (SABET =41 and 67 m2 gÀ1, respectively). Both ad-
ducts were isolated as mixtures of regioisomers and were
found to be highly soluble in common solvents (for example
Adducts 17 and 20, derived from the reaction between un-
substituted naphthalene-2,3-diol precursor (4a) and cores
1 and 2, respectively, gave poorly soluble materials with no ap-
parent microporosity (Table 1), similar to adducts 10 and 14
prepared using unsubstituted catechol (3a). X-ray crystallo-
graphic analysis of 10, 14, and 17 (Figure 4) demonstrates that
for each of these adducts there are extensive p–p interactions
between the aromatic arms causing the molecules to pack effi-
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Figure 3. Molecular structures of 10 (top) and 14 (bottom) obtained from
XRD analysis with their respective 19F NMR spectra, indicating total fluorine
substitution in 10 and the retention of a single fluorine atom on the middle
phenyl ring of the terphenyl unit in 14.
ciently, resulting in poor solubility and negligible porosity.
However, the use of tert-butyl substituted naphthalene-2,3-diol
(4b) as a precursor gave biphenyl 18 and terphenyl 21 with
significant apparent SABET of 260 and 259 m2 gÀ1, respectively.
This enhanced porosity is attributed to the tert-butyl substitu-
ents prohibiting close interactions between aromatic arms of
adducts resulting in less efficient packing.
Figure 4. X-ray crystal structures of 10 (top), 14 (middle), and 17 (bottom),
revealing p–p induced staking of the constituent molecules. Protons and
solvent molecules are removed for clarity.
Given its success as a component for making organic micro-
porous materials,[26] triptycene derived arms were also investi-
gated for making OMIMs. Hence, cores 1 and 2 were combined
with triptycene-2,3-diol (5a)[27] to give 23 (OMIM-1)[20b] and 28
(OMIM-10), respectively. Both OMIM-1 and OMIM-10 proved to
be highly soluble and gave amorphous solids with apparent
SABET of 485 and 423 m2 gÀ1, respectively. The addition of bulky
terminal substituents to give triptycene precursors 5c and 5e
enhances porosity in the resulting OMIMs, irrespective of
whether they are attached to a biphenyl (OMIM-4 and OMIM-
5) or terphenyl core (OMIM-12 and OMIM-14), with each dem-
ent SABET of 351 m2 gÀ1, as compared to 423 m2 gÀ1 for OMIM-
10. The values of SABET for the tert-butyl substituted analogues
(OMIM-12 and OMIM-13) also differ by a similar amount
(75 m2 gÀ1). It appears that the space adjacent to the bridge-
head in triptycene terminated OMIMs is directly contributing
to the porosity of the material, hence, filling this space with
a methyl group reduces the amount of intrinsic microporosity
that can be generated during the amorphous packing of the
molecules. Indirect evidence for this feature of amorphous
packing comes from the single-crystal XRD analysis of OMIM-
1 (Figure 5), which shows solvent-filled channels defined par-
tially by the triptycene bridgehead positions. Similar local or-
dering may occur within the amorphous packing of triptycene-
based OMIMs. Further XRD analysis of OMIM-1, OMIM-5, and
OMIM-8 is presented in the Supporting Information, Figure S2–
S4.
onstrating a high apparent SABET in the range 654–726 m2 gÀ1
.
OMIM-12 possesses intrinsic microporosity greater than many
PIMs and comparable to that of the archetypal PIM-1 (ca.
780 m2 gÀ1).[13a] OMIM-12 is of a similar porosity to a p-extend-
ed triptycene recently reported by the Mastalerz group
(SABET =754 m2 gÀ1),[20c] which were similarly designed to pack
inefficiently.
Notably, triptycene peripheral units substituted with methyl
groups at their bridgehead positions (5b, d) gave OMIMs with
lower apparent values of SABET relative to their non-methyl
containing counterparts. For example, OMIM-11 has an appar-
An investigation to determine the suitability of various rigid
structural building units as peripheral arms for OMIM construc-
tion was performed by combining catechol derivatives of ben-
zenopentacene (6)[20b] spirobifluorene (7),[28] propellane (8),[29]
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small, planar, non-substituted arms gave insoluble materials
with negligible surface areas (<30 m2 gÀ1). However, by using
arms composed of bulky rigid structural units, OMIMs were
prepared with apparent SABET in the range 333–612 m2 gÀ1. The
efficiency of unsubstituted structural units for generating mi-
croporosity is in the following order: propellane>triptycene>
hexaphenylbenzene>spirobifluorene>naphthyl=phenyl.
Substitution of these arms with bulky groups further enhanced
microporosity (up to 726 m2 gÀ1), which is presumably due to
reducing intermolecular cohesive interactions. In contrast, the
introduction of methyl groups at the bridgehead position of
triptycene units reduced intrinsic microporosity. In this case,
the internal position of the methyl groups within the OMIM
structure means that they occupy space but, unlike peripheral
substituents, cannot contribute to the generation of free
volume by frustrating packing.
Experimental Section
Example synthesis of adduct 10
4,4’-Dicyano-2,2’,3,3’,5,5’,6,6’-octafluorobiphenyl
(1;
0.230 g,
0.661 mmol) and catechol (3a) were added to an oven-dried flask
and purged with nitrogen. Anhydrous DMF (10 mL) was then
added via syringe and the reaction mixture heated to form a solu-
tion, at which point, oven dried potassium carbonate (0.306 g,
2.78 mmol) was quickly added, the reaction sealed under nitrogen
flow, heated to 658C and left to stir for 48 h. After cooling to room
temperature, the reaction mixture was poured into water (200 mL),
acidified with 2m HCl, and allowed to stir as a suspension for 2 h.
The crude product was then collected by filtration, washed with
water (200 mL) and methanol (200 mL), then dried under suction.
Purification of the crude material was achieved by column chroma-
tography (dichloromethane/hexane, 1:1, Rf =0.4) to give 10
(0.307 g, 74%) as a yellow powder (m.p.>3008C); IR (CH2Cl2 film)
Figure 5. Space filling view (top) and expanded view (bottom) of channels
running through OMIM-1.
1
2234, 1495, 1440, 1309, 1272, 1253 cmÀ1; H NMR (500 MHz, CDCl3):
d=7.00 (d, J=8.0 Hz, 4H, ArH), 6.96–6.93 (m, 4H, ArH), 6.88–6.85
(m, 4H, ArH), 6.66 ppm (d, J=8.0 Hz, 4H, ArH); 13C NMR (125 MHz,
CDCl3): d=141.1, 140.8, 140.0, 136.2, 125.3, 125.2, 117.0, 114.4,
110.6, 91.7 ppm (one carbon missing); HRMS (EI+, m/z) calc. for
C38H16N2O8: 628.0907 [M+], found 628.0903; GPC analysis (CHCl3)
Mn =548, Mw =578 gmolÀ1 relative to polystyrene, Mw/Mn =1.055;
BET surface area=7 m2 gÀ1; total pore volume=0.03 cm3 gÀ1 at p/
po =0.98. Crystallography data (CHCl3/MeOH): triclinic, space
and hexaphenylbenzene (9)[30] with cores 1 and 2. Benzeno-
pentacene containing OMIM-6 and OMIM-16, were found to
possess apparent SABET in the range 10–15% lower than their
more symmetrical isomeric triptycene-based counterparts
OMIM-5 and OMIM-14. It is probable that this is due to greater
intermolecular interactions between the long struts of the ben-
zenopentacene arms as compared to those of triptycene. From
an OMIM comparison, it can be concluded that the efficiency
of unsubstituted structural units for generating microporosity
is in the following order: propellane>triptycene>hexaphenyl-
benzene>spirobifluorene>naphthyl=phenyl. This is consis-
tent with findings from previously reported packing simulation
studies.[21]
¯
group=P1, a=11.0410(6) Š, b=11.3324(7) Š, c=14.2766(7) Š, a=
113.045(5), b=90.659(4), g=106.663(5), V=1559.14 Š3, Z=2, R1 =
4.01.
Full experimental details and spectroscopic data for all of the new
compounds are given in the Supporting Information.
CCDC 955894, 973327, 1406070, 1406071, 1406072, 1406073, and
1406074 contain the supplementary crystallographic data for this
paper. These data are provided free of charge by The Cambridge
Crystallographic Data Centre.
Conclusions
Molecular adducts, designed to possess well-defined concavi- Acknowledgements
ties, were synthesised using the reaction between fluorinated
biphenyl and terphenyl cores and peripheral arms chosen from
a diverse range of rigid structural units. The intrinsic micro-
porosity generated by the inefficient packing of these adducts
was evaluated using nitrogen sorption at 77 K. The use of
We are grateful for support from the EPSRC, UK(EP/
H024034and EP/K008102/2). We thank Prof. Coray Colina (Flori-
da State University) and Prof. Peter Budd (University of Man-
chester) for valuable discussions.
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Keywords: adsorption · aromatic nucleophilic substitution ·
microporous materials · molecular packing · triptycene
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Published online on January 11, 2016
Chem. Eur. J. 2016, 22, 2466 – 2472
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2472 ꢀ 2016 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim