Enriching the Reticular Chemistry Repertoire: Merged Nets Approach for the Rational Design of Intricate Mixed-Linker Metal-Organic Framework Platforms

Article abstract of DOI:10.1021/jacs.8b04745

Rational design and construction of metal-organic frameworks (MOFs) with intricate structural complexity are of prime importance in reticular chemistry. We report our latest addition to the design toolbox in reticular chemistry, namely the concept of merged nets based on merging two edge-transitive nets into a minimal edge-transitive net for the rational construction of intricate mixed-linker MOFs. In essence, a valuable net for design enclosing two edges (not related by symmetry) is rationally generated by merging two edge-transitive nets, namely (3,6)-coordinated spn and 6-coordinated hxg. The resultant merged-net, a (3,6,12)-coordinated sph net with net transitivity [32] enclosing three nodes and two distinct edges, offers potential for deliberate design of intricate mixed-linker MOFs. We report implementation of the merged-net approach for the construction of isoreticular rare-earth mixed-linker MOFs, sph-MOF-1 to -4, based on the assembly of 12-c hexanuclear carboxylate-based molecular building blocks (MBBs), displaying cuboctahedral building units, 3-c tritopic ligands, and 6-c hexatopic ligands. The resultant sph-MOFs represent the first examples of MOFs where the underlying net is merged from two 3-periodic edge-transitive nets, spn and hxg. Distinctively, the sph-MOF-3 represents the first example of a mixed-linker MOF to enclose both trigonal and hexagonal linkers. The merged-nets approach allows the logical practice of isoreticular chemistry by taking into account the mathematically correlated dimensions of the two ligands to afford the deliberate construction of a mixed-linker mesoporous MOF, sph-MOF-4. The merged-net equation and two key parameters, ratio constant and MBB constant, are disclosed. A merged-net strategy for the design of mixed-linker MOFs by strictly controlling the size ratio between edges is introduced.

Full text of DOI:10.1021/jacs.8b04745

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Article
Enriching the Reticular Chemistry Repertoire: Merged Nets Approach
for the Rational Design of Intricate Mixed-linker MOF Platforms.
Hao Jiang, Jiangtao Jia, Aleksander Shkurenko, Zhijie Chen, Karim Adil, Youssef Belmabkhout,
Lukasz J. Weselinski, Ayalew H. Assen, Dong-Xu Xue, Michael O'Keeffe, and Mohamed Eddaoudi
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.8b04745 • Publication Date (Web): 20 Jun 2018
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The merged-net approach for the rational construction of mixed-linkers MOFs; The merging of sph net and
hxg net into a new sph net for the construction of sph-MOFs
82x44mm (300 x 300 DPI)
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Enriching the Reticular Chemistry Repertoire: Merged Nets
Approach for the Rational Design of Intricate Mixed-linker
MOF Platforms
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Hao Jiang,† Jiangtao Jia,† Aleksander Shkurenko,† Zhijie Chen,† Karim Adil,† Youssef Belmabkhout,†
Łukasz J. Weselinski,† Ayalew H. Assen,† Dong-Xu Xue,† Michael O’Keeffe,‡ Mohamed Eddaoudi*,†
́
†Functional Materials Design, Discovery and Development Research Group (FMD3), Advanced Membranes and Porous Materials Center
(AMPMC), Division of Physical Sciences and Engineering (PSE), King Abdullah University of Science and Technology (KAUST),
23955-6900, Kingdom of Saudi Arabia
‡School of Molecular Sciences, Arizona State University, Tempe, Arizona 85287, United States
ABSTRACT: Rational design and construction of MOFs with intricate structural complexity are of prime importance in reticular
chemistry. We report our latest addition to the design toolbox in reticular chemistry, namely the concept of merged-nets based on
merging two edge-transitive nets into a minimal edge-transitive net for the rational construction of intricate mixed-linker MOFs. In
essence, a valuable net for design enclosing two edges (not related by symmetry) is rationally generated by merging two edge-
transitive nets, namely (3,6)-coordinated spn and 6-coordinated hxg. The resultant merged-net, (3,6,12)-coordinated sph net with net
transitivity [32] enclosing three nodes and two distinct edges, offers potential for deliberate design of intricate mixed-linker MOFs.
We report the implementation of the merged-net approach for the construction of isoreticular RE mixed-linker MOFs, sph-MOF-1
to 4, based on the assembly of 12-c hexanuclear carboxylate-based MBBs, displaying cuboctahedral building units, 3-c tritopic lig-
ands, and 6-c hexatopic ligands. The resultant sph-MOFs represent the first examples of MOFs where the underlying net is merged
from two 3-periodic edge-transitive nets, spn and hxg. Distinctively, the sph-MOF-3 represents the first example of a mixed-linker
MOF to enclose both trigonal and hexagonal linkers. The merged-nets approach allowed the logical practice of isoreticular chemistry
by taking into account the mathematically correlated dimensions of the two ligands to afford the deliberate construction of a mixed-
linker mesoporous MOF, sph-MOF-4. Merged-net equation and two key parameters, ratio constant and MBB constant, are disclosed.
Merged-net strategy for design of mixed-linker MOFs by strictly controlling the size ratio between edges is introduced.
istry and crystal chemistry.8 The past two decades have wit-
nessed the burgeoning of MOF chemistry with the design and
■ INTRODUCTION
Over the past two decades, metal-organic frameworks (MOFs),
construction of a large myriad of MOF materials based on the
a distinctive class of hybrid crystalline materials constructed by
reticulation of edge-transitive nets9 or their derived nets.10 In-
linking metal-based units (metal ions or metal clusters) with
deed, MOFs based on edge-transitive nets are the dominant
polytopic organic linkers, have attracted wide interest in aca-
class of materials in MOF chemistry due to the relative ease of
demia and industry alike due to their high degree of porosity,
their isoreticulation and functionalization, prompting their ex-
unique functionalized structures and readily modular construc-
ploration in myriad applications.2a, 9f, 11
tion.1 The MOFs’ readily adjustable pore system metrics and
Logically, expanding the rational design of MOFs to include
multiple distinct linkers based on the reticulation of multi-edge
nets is of prime importance as it offers the prospective to delib-
erately access intricate materials with assorted functionalities
needed for prospect applications.12 Nevertheless, the majority
of mixed-linker intricate MOFs encompassing multiple ligands
with distinct shapes and dimensions were realized primarily by
the tedious trial-and-error approach.13 Markedly, the practice of
isoreticulation for intricate MOF platforms based on multi-
edges nets remains an ongoing challenge as the connecting pol-
ytopic ligands are mathematical correlated and their relative ex-
pansion is interrelated and needs to be coordinated/synchro-
nized; i.e. it is critical to elect the appropriate combination of
linkers with suitable dimensions to afford the requisite net ex-
pansion and construct the looked-for isoreticular MOF.14 It is to
be noted that various relatively simple examples of mixed-
linker structures were reported by linking 0-periodic polyhedra
or by pillaring 2-periodic layers in an axial-to-axial fasion,15 or
functionality positions MOFs as ideal candidate porous materi-
als to address the enduring challenges pertinent to energy and
environmental sustainability such as gas storage,2 gas separa-
tion,3 catalysis,4 and chemical sensing.5
The institution of reticular chemistry paved the way for the de-
sign, discovery and development of novel functional crystalline
solid-state materials including MOFs.6 Principally, the molecu-
lar building block (MBB) approach has emerged as a remarka-
ble pathway toward the design and synthesis of novel functional
MOFs.7 Purposely, prior the assembly process, the desired geo-
metric and connectivity features, functionalities and properties
can be encompassed in preselected MBBs at the design stage.
Certainly, the prospective for the effective design is reliant on
the ability to access and deploy building blocks with geomet-
rical information and encoded connectivity affording the points
of extension to match the vertex figures of the targeted net. Con-
vincingly, edge-transitive nets (all edges are equivalent by sym-
metry) are regarded as suitable design targets in reticular chem-
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both parent nets and offering great prospective for the materials’
by inserting/placing a second linker into specific MOFs con-
taining “accepting” sites such as open metal sites16 or by ex-
changing terminal coordinating groups (e.g. hydroxide, acetate
or benzoate groups).17 Evidently, despite the notable success on
designing MOFs based on edge-transitive nets, the rational de-
sign of mixed-linker MOFs with higher complexity, in a pur-
poseful one-pot synthesis, using reticular chemistry has yet to
be demonstrated and rationalized.
designer. Practically, we envisioned that two frameworks can
merge together through a shared inorganic MBB, thus allowing
the successful practice of reticular chemistry for the design of
intricate mixed-linker MOFs. Accordingly, we conceived and
pursued some key perquisites for the plausible design of mixed-
linker MOFs: (i) the designate merged two MOFs are based on
minimal edge-transitive nets; (ii) the embedded partial frame-
works linking inorganic building units and each organic linkers
are based on edge-transitive nets; (iii) the two partial frame-
works have to merge and connect to each other via shared inor-
ganic MBBs.
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Our continuous quest to deploy practical strategies for the logi-
cal design of MOFs,10b, 15, 18 has prompted us to closely analyze
the edge-transitive nets with the aim to uncover a plausible cor-
relation/inter-relation between pairs of nets.19 Recently, we re-
marked the prominence of deploying highly-connected building
units in combination with minimal edge-transitive derived net
(transitivity [32]), based on splitting one type of vertex in the edge-
transitive net into groups of linked vertices of lower coordination
(e.g., one 12-c to one 6-c and one type of 3-c), as a powerful strat-
egy for the design and construction of MOFs where branched
ligands are employed for the deliberate access of the required and
intricate highly coordinated net-cBUs.10d, 20 Reasonably, we real-
ized that merging two edge-transitive nets (transitivity [21] or
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Here, we introduce a systematic design principle, named
merged net strategy, targeting the design of highly complex
mixed-linker MOFs. Notably, the relevance of this concept has
been asserted using a mathematical relationship, named merged
net equation, that take into consideration the inherent geomet-
rical features of the net that compose the resultant merged net.
Markedly, it is becoming evident the employed pair of linkers
need to be extended linearly, but not proportionally, in order to
construct isoreticular mixed-linker MOFs, addressing the long-
standing problem of reliable design of isoreticular mixed-linker
MOFs.
[11]) with the premise to afford shared nodes might lead to a
20
new minimal edge-transitive net8,
(transitivity [32]) with
higher complexity, encompassing the structural properties from
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Figure 1. Schematic representation showing the assembly of sph-a net and the sph-MOF with sph-MOF-3 as an example. (a) The
12-c cuboctahedral building unit can be split into two groups, namely, 6-c trigonal antiprism and 6-c hexagonal building unit. (b) The
corresponding RE hexanuclear cluster shown in atom mode (left) and polyhedral mode (middle and right). (c) Linking the split
building units with triangular and hexagonal building unit results in the formation of spn-a net and hxg-a net. (d) The corresponding
spn and hxg partial framework assembled from BTTC and BHPB linker. (e) The spn-a net and hxg-a net merge to form sph-a net.
(f) The corresponding spn and hxg partial frameworks merge to sph-MOF. RE, C, O and S are represented by purple, grey, red and
dark yellow, respectively, and H atoms are omitted for clarity. Cages are illustrated with yellow and green balls.
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3-periodic edge-transitive nets. In addition, the sph-MOF-3
The election of building units with the requisite connectivity
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2
3
4
5
6
7
8
and geometrical information, coding the targeted net, is central
to the practice of reticular chemistry and the design of MOFs.21
For instance, the augmentation of the (3,6)-coordinated spn net
permits the identification of the spn net vertex figures as the 3-c
trigonal and the 6-c trigonal antiprismatic, and subsequently
provides the coded information embedded in the building units
for the reticulation of the spn-a net. Similarly, the uninodal
6-coordinated hxg net requires hexagonal building unit for its
prospective reticulation. However, a plausible relationship/con-
nection between the aforementioned two edge-transitive nets
was not evident and a possible conjunction of their associated
building units was unfortunately dismissed and not considered
over the past two decades. Actually, the juxtaposition of the
trigonal antiprism (a building unit of spn net) and the hexagon
(a building unit of hxg net) results in a cuboctahedral building
unit; i.e. the cuboctahedral building unit offers two prospective
building units by deliberately separating the points of extension
into two sets to give the trigonal antiprism (a building unit of
spn net) and the hexagon (a building unit of hxg net). Propos-
edly, each set of points of extension can be linked to additional
building units (triangle for spn net and hexagon for hxg net) to
form a 3-periodic net, asserting the potential to employ the cub-
octahedral building unit for the introduction of the spn and hxg
nets at the same time in the same resultant 3-periodic structure.
represents the first example of a mixed-linker MOF encompass-
ing both a 3-c trigonal linker and a 6-c hexagonal linker. Our
introduced merged nets approach allowed the logical practice
of isoreticular chemistry, the expansion of the 3-c and 6-c pol-
ytopic ligands was done in a concerted fashion, taking into ac-
count the mathematically correlated dimensions of the two lig-
ands, to afford the deliberate construction of a mixed-linker
mesoporous MOF, sph-MOF-4, with cage dimension of 22 Å
as confirmed by argon sorption studies.
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■ RESULTS AND DISCUSSION
Synthesis of single-linker Tb-spn-MOF-1. Various polycar-
boxylate ligands were explored with the aim to construct a pro-
totype MOF that is amenable to the rational design of mixed-
linker MOFs. During the screening of different ligands, an spn-
MOF was obtained based on Terbium and 5-(4H-1,2,4-triazol-
4-yl)-isophthalate (TIA), which provided the opportunity for
the design of mixed-linker MOFs based on sph net.
Solvothermal reactions of Tb(NO3)3·5H2O and H2TIA in a N,N-
dimethylformamide (DMF)/water solution in the presence of 2-
fluorobenzoic acid (2-FBA) for 48 hours at 115 °C yielded col-
orless octahedral single crystals of Tb-spn-MOF-1. Single-
crystal X-ray diffraction studies (SCXRD) revealed the com-
pound crystallized in the cubic space group Fd-3m with a unit
cell parameter a = 38.309(4) Å. The compound formulated as
[Tb6(μ3-OH)8(TIA)2(2-FBA)6(H2O)6]·(solv)x, which is also
confirmed by thermogravimetric (TGA) (Figure S9, right) and
elemental analysis. The phase purity of the crystalline material
was confirmed by the similarities between the calculated pow-
der X-ray diffraction (PXRD) pattern derived from the associ-
ated SCXRD data and the experimental PXRD pattern of the as-
synthesized material (Figure S9, left).
Practically, the precise control of the ratio between the associ-
ated edges of the spn and hxg nets, all trigonal antiprism build-
ing units in the spn net and half of the hexagonal building units
in the hxg net can merge to form cuboctahedral building units.
As a result, the two edge-transitive nets, (3,6)-c spn net (transi-
tivity [21]) and 6-c hxg net (transitivity [11]), can perfectly
merge to form a new minimal edge-transitive (3,6,12)-c net
(transitivity [32]) with higher complexity, we named sph net
(“sp” from “spn” and “h” from “hxg”). The concept of merging
two 3-periodic edge-transitive nets to afford a new minimal
edge transitive sph net offers great potential for the deliberate
design of sph-MOF platforms.
It is worth mentioning that Tb-spn-MOF-1 is the first spn-MOF
constructed by lower symmetric TIA linkers with two carbox-
ylate group and one triazole group. In the structure of Tb-spn-
MOF-1, each inorganic MBB is connected to six TIA linkers,
and each of the linkers is coordinated to three inorganic MBBs.
In addition, each inorganic MBB is also coordinated to six 2-
fluorobenzoate, terminal ligands, which account for the charge
balance.
Rationally, our recently introduced 12-c cuboctahedron build-
ing units based on the 12-connected rare-earth (RE) hexanu-
clear [RE6(μ3-OH)8(μ3-O)2(O2C−)12] carboxylate-based cluster
inspired us to pursue the design of mixed-linker MOF platforms
based on the reticulation of sph net.22 To put into practice the
merged nets approach for the design of mixed-linkers sph-MOF
platform, we derived some key prerequisites in addition to the
deployment of the rare earth hexanuclear clusters as the requi-
site12-c cuboctahedral MBB: (i) 3-c trigonal MBB provided by
tricarboxylate ligands, (ii) 6-c hexagonal MBB, afforded by
predesigned hexacarboxylate ligands or two π-π interacting 3-c
tricarboxylate ligands, (iii) derive the mathematical equation
that defines the relationship between the dimensions of the req-
uisite 3-c and 6-c organic MBBs.
Structural and topological analysis revealed that the hexanu-
clear terbium cluster, a 6-c MBB, linked to the ligand TIA, a
3-c MBB, to form a 3-periodic MOF with the underlying (3,6)-c
spn net. The 1,3,5-position carbon atoms of the benzene ring of
TIA are acting as points of extension of the 3-c node. The car-
bon atoms of the coordinated carboxylate moieties and the 1-
position nitrogen atoms of the coordinated triazole moieties are
acting as points of extension of the 6-c node. The overall frame-
work of Tb-spn-MOF-1 contains two types of cages. The larger
cages are about 19.5 Å in diameter, while the smaller cages have
an internal pore diameter of about 5.4 Å and are delimited by
four TIA linkers.
Certainly, a series of highly symmetric isoreticular mixed-
linker MOFs, sph-MOF-1 to 4, were rationally designed and
synthesized based on the assembly of 12-c hexanuclear carbox-
ylate-based MBBs, displaying cuboctahedral building units, 3-c
tritopic ligands, and 6-c hexatopic ligands or π-π interacting
paired 3-c tritopic ligands. Markedly, it is to be noted that the
sph-MOF platform represents the first example where the un-
derlying net is a minimal edge-transitive net merged from two
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Figure 2. Schematic showing the design of sph-MOFs by utilizing the merged net equation. (a) When the edge ratio between spn
and hxg nets exactly meet the constant, the two nets can merge to sph net. (b) The size of half Tb hexanuclear cluster is 4.7 Å. (c)
The merged net equation shows the relationship between spn and hxg linkers. (d) The size of both linkers in sph-MOFs could be
designed from the merged net equation.
푥
푦
( )
ퟏ
=
휋
6
2휋
Design of mixed-linker sph-MOF platform based on merged
net. The analysis of the crystal structure of Tb-spn-MOF-1 re-
vealed that it possesses the appropriate structural features for
accepting a second linker using the traditional installation meth-
odology. More importantly, the careful analysis of the resulted
MOF drew our attention that the partial framework based on the
sole second linkers can also be described as a 3-periodic frame-
work with an underlying edge-transitive hxg net. In other
words, the underlying net of resultant mixed-linker MOF can be
deconstructed into two different nets, namely spn net and hxg
net by taking into consideration that the cuboctahedron building
unit can be deconstructed into a trigonal antiprism and a hexa-
gon building unit. Concretely, the underlying net of the targeted
framework is merged from both parent nets (Figure 1a-c). Ac-
cordingly, the mixed-linker MOFs with variable sizes can be
directly designed based on the underlying merged net by utiliz-
ing the knowledge of reticular chemistry.
sin ( )
sin (
)
3
From the equation (1), the dimension ratio of edges between the
spn net and the hxg net is a constant, which is an intrinsic prop-
erty of sph net. Namely, spn and hxg nets can merge to sph net
only when their edge ratio meets a constant, noted ratio constant
CR.
푥
푦
3
√
( )
ퟐ C
=
=
R
3
Alternatively, the approximate value of ratio constant CR could
also be calculated from the coordinate of nodes of the sph net,
which we deposited in the Reticular Chemistry Structural Re-
source (RCSR) database.24 Set the coordinates of 3-c node as
(a1, b1, c1), the coordinates of 6-c node as (a2, b2, c2), and the
coordinates of 12-c node as (as, bs, cs), then,
(a -a )2+(b -b )2+(c -c )2
√
1
s
1
s
1 s
( )
ퟑ C
=
The topological analysis revealed that the perceived mixed-
linkers MOF adopts a new underlying net that we called sph.
The rationalization of this merging process was demonstrated
mathematically using a geometrical based relationship that
takes into consideration the inherent geometrical features of the
sph net. Indeed, the analysis/deconstruction of the resultant sph
net shows a clear correlated relationship between the dimen-
sion/length of the associated edges of spn and hxg nets, respec-
tively set up as x and y (Figure 2a). Precisely, the relationship
between x and y could be calculated according to the Law of
sines as depicted in Figure S2:
(a -a )2+(b -b )2+(c -c )2
R
√
2
s
2
s
2 s
Obviously, the ratio constant CR is the key factor for determin-
ing the dimensions of linkers in mixed-linker sph-MOFs. How-
ever, it is worth taking into consideration that the size ratio be-
tween the edges of two parent nets is not equal to the size ratio
of just ligands but the sum of ligands and half MBBs (Figure
2b). The merged net equation of sph net is as exemplified by
the following equation (4).
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and topological analysis revealed that two tricarboxylate linkers
퐿spn + CM
퐿hxg + CM
( )
ퟒ
= CR ,
1
2
BTCB are packed together and serve as a 6-c MBB. The hexa-
nuclear terbium cluster, a 12-c MBB, linked to the ligand TIA,
a 3-c MBB, and the paired BTCB moiety, a 6-c MBB, to form
a 3-periodic (3,6,12)-c MOF with the unprecedented sph under-
lying topology. The 1,3,5-position carbon atoms of the benzene
ring of TIA are acting as points of extension of the 3-c nodes.
The 1,3,5-position carbon atoms of the center benzene ring of
double BTCB moieties are acting as points of extension of the
6-c node. The carbon atoms of the coordinated carboxylate moi-
eties and the 1-position nitrogen atoms of the coordinated tria-
zole moieties are acting as points of extension of the 12-c node.
As anticipated, by further topologically analysis of sph-MOF-
1, the underlying (3,6,12)-c sph net was found to be an assem-
bly of two edge-transitive nets, (3,6)-c spn net and 6-c hxg net.
3
4
5
6
7
8
9
where Lspn is the length from the center of the 3-c linker to the
corresponding carbon atom of carboxylate group, Lhxg is the
length from the center of the 6-c linker to the corresponding
carboxylate carbon atom, and CM is the constant size defined as
the half size of the MBB, length calculated from carboxylate
carbon to the center of the cluster. In the case of terbium hexa-
nuclear MBB, the MBB constant CM is equal to ca. 4.7 Å by
assessing the reported structures.9e, 22, 25 Practically, by introduc-
ing this value of CM into the merged net equation of sph net (4),
the relationship between Lspn and Lhxg can be clarified:
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( )
ퟓ 퐿spn= 0.58 퐿hxg – 2.0 Å
The overall framework of sph-MOF-1 contains two types of
open cages. The larger truncated tetrahedral cages, having di-
ameters of about 6.5 Å, are delimited by four pairs of BTCB
and four TIA linkers, while the smaller tetrahedral cages, hav-
ing diameters of about 2.5 Å, which are inaccessible by nitrogen
or argon, are delimited by four TIA linkers (Figure S6). The
corresponding solvent accessible volume for sph-MOF-1 was
estimated to be 54%, by summing voxels more than 1.2 Å away
from the framework using PLATON software.23
or
퐿hxg= 1.73 퐿spn + 3.5 Å.
By employing equation (5), the materials’ designer can deter-
mine the appropriate size of the complementary linker needed
for the design of the looked-for mixed-linker sph-MOF. More-
over, this equation (5) also determines the condition of applying
the isoreticular chemistry within the mixed-linker system as ex-
emplified here by the design of four new compounds, namely
sph-MOF-1, 2, 3 and 4 (Figure 2d). By checking the size of
available 3-c or 6-c linkers, four pairs of ligands based on three
pairs of different sizes were predicted to be precisely matching
the sph net and consequently allowed us to deliberately synthe-
size their corresponding mixed-linker sph-MOFs (Figure 3).
The permanent porosity of sph-MOF-1 has been examined by
argon adsorption experiment carried out at 87 K, exhibiting a
fully reversible type-I isotherm characteristic of microporous
materials (Figures S14-16). The apparent Brunauer-Em-
mett−Teller (BET) surface area and Langmuir surface area were
estimated to be 1020 m2·g− 1 and 1120 m2·g− 1, respectively. The
experimental total pore volume was calculated to be 0.37
cm3·g− 1, which is consistent with the theoretical pore volume
of 0.44 cm3·g− 1, based on the associated crystal structure.
Design and synthesis of sph-MOF-1. Based on previous re-
sults, TIA was chosen as the first linker of spn part for the syn-
thesis of sph-MOF-1. The size of TIA linker can be calculated
as 3.5 Å based on the weighted average value since the linker is
asymmetrical. The corresponding size of the hxg linker can be
calculated by the merged net equation as 9.5 Å, which is match-
ing with the acylamide-functionalized group based linker (Fig-
ure 3b).
Design and synthesis of sph-MOF-2. The successful design of
sph-MOF-1 proofed the effectiveness of the merged net equa-
tion, defining the mathematical correlation between the two
linkers, and encouraged us to explore isoreticular sph-MOFs
with expanding linkers to afford relatively larger cages. Ac-
cording to the merged net equation of the sph net, if sizes of
both linkers are linearly increasing by a coefficient of 1.73, the
resulted linker pair will still be suitable for the synthesis of sph-
MOFs. Precisely, the linker responsible for the spn net can be
expanded by 1.0 Å if the corresponding hxg linker is increased
by 1.73 Å. Based on this principle, a second linker pair was
elected. Indeed, the size (5.1 Å) of linker benzo-tris-thiophene
carboxylate (BTTC) was found to be matching with the size
(12.3 Å) of linker 4,4',4''-(benzene-1,3,5-triyl-tris(benzene-4,1-
diyl))tribenzoate (BTPB) (Figure 3).
However, our attempts to obtain the corresponding hexacarbox-
ylate linker was unsuccessful due to the encountered synthetic
difficulties in inserting six acylamide functional moieties into
one benzene ring. Instead, a tricarboxylate linker 4,4',4''-((ben-
zene-1,3,5-tricarbonyl) tris(azanediyl)) tribenzote (BTCB) was
synthesized and used since the packing of two BTCB linkers
could possibly serve as a 6-c building block (Figure S3).
As expected, solvothermal reactions of Tb(NO3)3·5H2O, H2TIA
and H3BTCB in a DMF/water solution in the presence of 2-FBA
for 48 hours at 115ꢀ°C yielded colorless octahedral single crys-
tals of sph-MOF-1. The SCXRD studies revealed that the com-
pound crystallized in the cubic space group Fd-3m with a unit
cell parameter a = 38.985(5) Å. The compound formulated as
[Tb6(μ3-OH)8(TIA)2(BTCB)2(H2O)6]·(solv)x, which is also con-
firmed by TGA (Figure S10, right) and elemental analysis. The
phase purity of the bulk crystalline materials for sph-MOF-1
was confirmed on the basis of similarities between the calcu-
lated and as-synthesized PXRD patterns (Figure S10, left). The
presence of linkers TIA and BTCB were also confirmed by 1H
NMR of the HCl digested samples (Figure S31).
As expected, solvothermal reactions of Tb(NO3)3·5H2O,
H3BTTC, and H3BTPB in a DMF/water solution in the presence
of 2-FBA for 48 hours at 115ꢀ°C yielded colorless octahedral
single crystals of sph-MOF-2. The SCXRD studies revealed
that sph-MOF-2 crystallized in the cubic space group Fd-3 with
a unit cell parameter a = 45.6614(5) Å. The compound formu-
lated as [(CH3)2NH2]2[Tb6(μ3-OH)8(BTTC)2(BTPB)2(H2O)6]
(solv)x, which is also confirmed by TGA (Figure S11, right)
and elemental analysis. The presence of linkers BTTC and
1
BTPB were also confirmed by H NMR of the HCl digested
In the structure of sph-MOF-1, each Tb6 cluster links to twelve
linkers in two groups. Six TIA linkers occupied the trigonal an-
tiprism position of the cuboctahedron, and six BTCB linkers
occupied the planar hexagonal positions (Figure S3). Structure
samples (Figure S32). The experimental PXRD is consistent
with the PXRD pattern calculated based on the crystal structure,
which confirmed the phase purity of sph-MOF-2 (Figure S11,
left).
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Figure 3. Schematic showing the ligands used in the synthesis of sph-MOFs, (a) ligands of the spn partial frameworks, the sizes
showing distances from the center of linkers to the carboxylic carbon or the center of triazole; (b) ligands of the hxg partial frame-
works; (c) structures of sph-MOF-1 to 4.
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In the structure of sph-MOF-2, each 12-c Tb6 cluster links to
can be viewed as points of extension of the 3-c triangular
2
twelve linkers in two groups. Six 3-c BTTC linkers occupied
the trigonal antiprism position of the cuboctahedron, and six
3-c BTPB linkers occupied the planar hexagonal position
(Figure 1a, 4). The paired BTPB moiety works as a 6-c MBB
to form a 3-periodic MOF with the underlying (3,6,12)-c sph
net, which is isoreticular to sph-MOF-1. The carbon atoms,
which are adjacent to the sulfur atoms in BTTC, are acting as
points of extension of the 3-c nodes. The 1,3,5-position carbon
atoms of the center benzene ring of double BTPB moieties are
acting as points of extension of the 6-c nodes. For the 12-c
nodes, unlike the nodes in sph-MOF-1, which has points of
extension from both carboxylate moieties and triazole moie-
ties, only the carbon atoms of the coordinated carboxylates are
acting as points of extension in sph-MOF-2.
node. The 1,2,3,4,5,6-position carbon atoms of the center ben-
zene ring of BHPB moieties can be considered as points of
extension of the 6-c hexagonal node. The carbon atoms from
the coordinated carboxylates can be regarded as points of ex-
tension of the 12-c cuboctahedral node in sph-MOF-3. Com-
paring to sph-MOF-2, the 6-c BHPB linker makes the struc-
ture of sph-MOF-3 more regimented with less rotation of the
cluster, which can be clearly seen from the horizontal view of
the linker (Figure 4).
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The overall framework of sph-MOF-3 also contains two types
of open cages. The larger truncated tetrahedral cages are de-
limited by four BHPB and four BTTC linkers. The diameters
of the large cages are about 13 Å, which are slightly larger
than sph-MOF-2 since the BHPB linkers occupy less space
than two BTCB linkers (Figure 4b, 4d). The smaller tetrahe-
dral cages, having diameters of about 6.5 Å, are enclosed by
four BTTC linkers (Figure S6). The corresponding solvent ac-
cessible volume for sph-MOF-3 was estimated to be 65%, by
summing voxels more than 1.2 Å away from the framework
using PLATON software.23
As a result of the linker extension, both of the open cages in
sph-MOF-2 are enlarged. The larger truncated tetrahedral
cages, having diameters of about 12.5 Å, are delimited by four
pairs of BTPB and four BTTC linkers. The smaller tetrahedral
cages, having diameters of about 6.5 Å, are enclosed by four
BTTC linkers (Figure S6). The corresponding solvent acces-
sible volume for sph-MOF-2 was estimated to be 64%, by
summing voxels more than 1.2 Å away from the framework
using PLATON software.23
The permanent porosity of sph-MOF-2 has been examined by
argon adsorption experiment at 87K, showing a fully reversi-
ble type-I isotherm characteristic (Figures S17-19) of a mi-
croporous material. The apparent BET surface area and Lang-
muir surface area were estimated to be 1820 m2·g− 1 and 2000
m2·g− 1, respectively. The experimental total pore volume was
estimated to be 0.67 cm3·g− 1, which is consistent with the the-
oretical pore volume of 0.70 cm3·g− 1, based on the associated
crystal structure.
Design and synthesis of sph-MOF-3. The calculated size
(12.3 Å) of hxg linker provides the opportunity to synthesize
sph-MOFs with the 6-c ligand. Instead of H3BTPB in sph-
MOF-2, a hexacarboxylate ligand hexakis(4-(4-carboxy-
phenyl) phenyl) benzoic acid (H6BHPB) was designed and
synthesized. The BHPB linker remains the same size as BTCB
and matches with BTTC (5.1 Å) for the merged net equation.
Solvothermal reactions of Tb(NO3)3·5H2O and H3BTTC,
H6BHPB in a DMF/water solution in the presence of 2-FBA
for 48 hours at 115ꢀ°C yielded colorless octahedral single
crystals of sph-MOF-3. The SCXRD studies revealed that
sph-MOF-3 crystallized in the cubic space group Fd-3m with
a unit cell parameter a = 46.0411(4) Å, which is about 0.4 Å
larger than sph-MOF-2. The compound formulated as
[(CH3)2NH2]2[Tb6(μ3-OH)8(BTTC)2(BHPB)(H2O)6]·(solv)x,
which is also confirmed by TGA (Figure S12, right) and ele-
mental analysis. The presence of linkers BTTC and BHPB
were also confirmed by 1H NMR of the HCl digested samples
(Figure S33). The phase purity of the bulk crystalline materi-
als for sph-MOF-3 was also confirmed on the basis of simi-
larities between the calculated and as-synthesized PXRD pat-
terns (Figure S12, left).
Figure 4. Schematic showing the comparison between sph-
MOF-2 and sph-MOF-3. The difference of chemical environ-
ment between BTPB and BHPB linker in sph-MOF-2 and
sph-MOF-3 are shown in (a) top view and (b) horizontal view.
Correspondingly, the shape and size of cages, (c) small tetra-
hedral cages and (d) large truncated tetrahedral cages, are also
slightly tuned from sph-MOF-2 to sph-MOF-3.
The topological analysis of sph-MOF-3 showed that the hex-
anuclear terbium cluster, a 12-c MBB, linked to the ligand
BTTC, a 3-c MBB, and the ligand BHPB, a 6-c MBB, to form
a 3-periodic MOF with the underlying (3,6,12)-c sph net,
which is isoreticular to sph-MOF-1and sph-MOF-2. The car-
bon atoms, which are adjacent to the sulfur atoms in BTTC,
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The permanent porosity of sph-MOF-3 has been examined by
argon adsorption experiment at 87K, showing a fully reversi-
ble type-I isotherm (Figures S20-22) characteristic of a mi-
croporous material. The apparent BET surface area and Lang-
muir surface area was estimated to be 1930 m2·g− 1 and 2250
m2·g− 1, respectively. The experimental total pore volume was
estimated to be 0.72 cm3·g−1, which is consistent with the the-
oretical pore volume of 0.73 cm3·g− 1, based on the associated
crystal structure.
Page 10 of 12
The apparent BET surface area was estimated to be 2170
m2·g− 1. The experimental total pore volume was estimated to
be 1.14 cm3·g− 1, which is consistent with the theoretical pore
volume of 1.27 cm3·g− 1, based on the associated crystal struc-
ture.
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Design and synthesis of mesoporous sph-MOF-4. In order
to test the effectiveness of merged net equation for the design
of mesoporous MOFs, sizes of both linkers are further ex-
tended. The linker 4,4',4''-s-Triazine-2,4,6-triyl-tribenzoate
(TATB) with size about 7.4 Å and the linker 4,4',4''-(benzene-
1,3,5-triyl-tris(biphenyl-4,4'-diyl))tribenzoate (BTBPB) with
size about 16.3 Å was found to match the equation. It is worth
mentioning that no structure has been reported with BTBPB
linker by searching the Cambridge Structural Database
(CSD),26 which reveals the difficulty of obtaining MOFs with
such an elongated tricarboxylate linker.
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As anticipated, solvothermal reactions of Tb(NO3)3·5H2O and
H3TATB, H3BTBPB in a DMF solution in the presence of 2-
FBA for 48 hours at 115 °C yielded colorless octahedral sin-
gle crystals of sph-MOF-4. The SCXRD studies revealed that
sph-MOF-4 crystallized in tetragonal space group I41 with a
unit cell a = b = 39.740(1) and c = 56.261(2). The compound
formulated as [(CH3)2NH2]2[Tb6(μ3-OH)8(TATB)2(BTBPB)2
(H2O)6]·(solv)x, which is also confirmed by TGA (Figure S13,
right) and elemental analysis. The presence of linkers TATB
and BTBPB were confirmed by 1H NMR of the HCl digested
samples (Figure S34). The phase purity of the bulk crystalline
sph-MOF-4 was confirmed by similarities between the calcu-
lated and as-synthesized PXRD patterns (Figure S13, left).
Figure 5. Ar adsorption isotherm at 87K of Tb-sph-MOFs.
Gas Sorption Studies of sph-MOF-1. In light of the known/
existing large library of adsorption data on MOFs and their
relationships to important applications like CO2 separation3
and natural gas upgrading,27 we aimed to access single gas ad-
sorptive performance of Tb-sph-MOF-1 in this mixed-linker
system and evaluate the adsorption properties relationships as
compared to the MOF benchmarks. The isosteric heat of ad-
sorption (Qst), calculated using CO2 adsorption isotherms at
258, 273, 288 and 298 K (Figures S26-27), show a decreasing
tendency. The Qst value at low loadings is 29.4 kJ mol-1, fur-
ther leveling off at the typical value for pore filling, shows that
the acylamide functionality in Tb-sph-MOF-1 generate the
same energetic effect in the pores reported in other acylamide
The topological analysis of sph-MOF-4 revealed that the 12-
c hexanuclear terbium clusters are linked to the 3-c TATB lig-
ands and the 6-c paired BTBPB moieties to form a 3-periodic
MOF with the underlying (3,6,12)-c sph net (Figure 1, Figure
S5). The carbon atoms of the center triazine in TATB can be
regarded as points of extension of the 3-c nodes. The 1,3,5-
position carbon atoms of the center benzene ring of double
BTBPB moieties can be viewed as points of extension of the
6-c nodes. The carbon atoms of the coordinated carboxylates
can be presented as points of extension of the 12-c nodes. The
successful synthesis of the isoreticular structure sph-MOF-4
demonstrated the effectiveness of our mathematic calculation,
even when the size of linkers are highly expanded.
based MOFs.28 Further, light hydrocarbon adsorption (CnH2n+2
i.e. C2H6, C3H8, n-C4H10 and iso-C4H10) as compared to CO2,
CH4 and N2 in wide range of pressure (Figures S28-S30) show
that mixed ligand based sph MOF platform, having the most
confined pore system show a typical enhancement behavior of
affinity as function or elevating the polarizabilities of the
probe molecules. This exemplified in CO2 having less adsorp-
;
The extension of the linkers provides both microporous cages
and mesoporous cages in the structure of sph-MOF-4. The
larger truncated tetrahedral cages, having diameters of about
22 Å, are delimited by four pairs of BTBPB and four TATB
linkers, while the smaller tetrahedral cages, having diameters
of about 9.5 Å, are enclosed by four TATB linkers (Figure
S6). The corresponding solvent accessible volume for sph-
MOF-4 was estimated to be 75%, by summing voxels more
than 1.2 Å away from the framework using PLATON soft-
ware.23
tion affinity to the Tb-sph-MOF-1 framework than CnH2n+2
,
similar to Rare-earth fcu-based MOFs25, 29 and divergent for
typical 13X zeolites. The above reported adsorption results,
demonstrate that tuning and exploring further the mixed lig-
and sph platform, could lead to powerful separation, storage
and sensing agents.
■ CONCLUSION
We introduced and described a new and systematic design
principle in reticular chemistry, named merged nets approach,
asserting the suitability of minimal edge-transitive nets
merged from edge-transitive nets as ideal blueprints for the
design of intricate mixed-linker MOFs. The fundamental
The permanent porosity of sph-MOF-4 has been examined by
argon adsorption experiment at 87K (Figures S23-25). An in-
crease at p/p0 = 0.25 on the argon adsorption isotherm corre-
sponds to a mesoporous cage of ca. 2.2 nm in sph-MOF-4.
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room temperature. The colorless polyhedral crystals were col-
equation, merged net equation, revealed the law of net merg-
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ing and solved the long-held problem of reliably designing
isoreticular mixed-linker MOFs.
lected and washed with DMF. The as-synthesized material
was found to be insoluble in H2O and common organic sol-
vents. FT-IR (4000−650 cm−1): 3399 (br), 2929 (w) 1652 (s),
1604 (s), 1517 (m) 1385 (vs), 1253 (m), 1094 (m), 1004 (w),
833 (w), 786 (s), 735 (m), 702 (m). Elemental analysis found
(calculated) for Tb6C124N2H106O43S6: C%: 41.1 (43.1), H%:
3.24 (3.09), N%: 0.98 (0.81).
We reported the design and construction of a series of highly
symmetric isoreticular RE mixed-linker MOFs, sph-MOF-1
to 4, based on the assembly of 12-c hexanuclear carboxylate-
based MBBs, displaying cuboctahedral building units, 3-c tri-
topic ligands, and 6-c hexatopic ligands or π-π interacted
paired 3-c tritopic ligands. The sph-MOFs represent the first
examples of MOFs where the underlying net is merged from
two 3-periodic edge-transitive nets, (3,6)-c spn net and 6-c
hxg net.
Synthesis of Tb-sph-MOF-3 (4). Tb(NO3)3·5H2O (8.3 mg,
0.0191 mmol), H3BTTC (2.5 mg, 0.0066 mmol), H6BHPB
(5.0 mg, 0.0039 mmol), 2-FBA (75.0 mg, 0.535 mmol), DMF
(1.5 ml), H2O (1.5 ml) and 3.5M HNO3 (0.2ml) were com-
bined in a 20 ml scintillation vial, sealed and heated to 115oC
for 48 h and cooled to room temperature. The colorless poly-
hedral crystals were collected and washed with DMF. The as-
synthesized material was found to be insoluble in H2O and
common organic solvents. FT-IR (4000−650 cm−1): 3209 (br),
1651 (m), 1603 (m), 1557 (m), 1392 (vs), 1178 (w), 1099 (m),
1005 (w), 838 (w), 776 (s), 736 (m), 703 (m). Elemental
analysis found (calculated) for Tb6C118N2H98O42S6: C%: 39.8
(42.1), H%: 2.91 (2.94), N%: 0.74 (0.83).
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The sph-MOF-3 represents the first example of a mixed-
linker MOF based on the assembly of the trigonal linker and
hexagonal linker. By concerted extension of both linkers, a
mesoporous mixed-linker MOF, sph-MOF-4, was con-
structed to enclose cages with a diameter of about 22 Å.
The noted unique control using merged nets to access intricate
mixed-linkers MOFs paves the way for the development of
advanced made-to-order MOFs with encoded distinct func-
tionalities. Work is in progress to enumerate other merged
nets form pairs of edge-transitive nets, prospectively enrich-
ing the reticular chemistry repertoire.
Synthesis of Tb-sph-MOF-4 (5). Tb(NO3)3·5H2O (7.5 mg,
0.0173 mmol), H3TATB (2.5 mg, 0.0057 mmol), H3BTBPB
(5.0 mg, 0.0055 mmol), 2-FBA (75.0 mg, 0.535 mmol) and
DMF (1.5 ml) were combined in a 20 ml scintillation vial,
sealed and heated to 115oC for 48 h and cooled to room tem-
perature. The colorless polyhedral crystals were collected and
washed with DMF. The as-synthesized material was found to
be insoluble in H2O and common organic solvents. FT-IR
(4000−650 cm−1): 3027 (br), 1651 (w), 1600 (m), 1507 (s),
1398 (vs), 1355 (vs), 1101 (w), 1017 (w), 1003 (w), 816 (s),
775 (vs), 700 (s). Elemental analysis found (calculated) for
Tb6C178N8H218O54: C%: 46.7 (49.8), H%: 4.97 (5.13), N%:
2.69 (2.61).
■ EXPERIMENTAL SECTION
Synthesis
of
single-linker
Tb-spn-MOF-1
(1).
Tb(NO3)3·5H2O (50 mg, 0.115 mmol), H2TIA (13 mg, 0.058
mmol), 2-FBA (300 mg, 2.14 mmol), DMF (1.5 ml) and H2O
(0.25 ml) were combined in a 20 ml scintillation vial, sealed
and heated to 115oC for 48 h and cooled to room temperature.
The colorless polyhedral crystals were collected and washed
with DMF. The as-synthesized material was found to be in-
soluble in H2O and common organic solvents. FT-IR
(4000−650 cm−1): 3383 (br), 1650 (s), 1610 (s), 1484 (m),
1451 (s) 1384 (vs), 1299 (w), 1252 (m), 1217 (m), 1161 (w),
1095 (s), 1058 (w), 1010 (w), 858 (w), 796 (w), 760 (s), 734
(m), 710 (m). Elemental analysis found (calculated) for
Tb6C65N7H55O29F6: C%: 31.1 (31.6), H%: 1.99 (2.25), N%:
4.06 (3.98).
ASSOCIATED CONTENT
Supporting Information
Detailed procedures for PXRD, TGA, NMR, the synthesis of the
organic ligands, additional structural figures, detailed topological
analysis, low- and high-pressure gas adsorption isotherms and X-
ray crystallographic data. This material is available free of charge
via the Internet at http://pubs.acs.org.
Synthesis of Tb-sph-MOF-1 (2). Tb(NO3)3·5H2O (50 mg,
0.115 mmol), H2TIA (13 mg, 0.058 mmol), H3BTCB (33 mg,
0.058 mmol), 2-FBA (300 mg, 2.14 mmol), DMF (1.5 ml) and
H2O (0.25 ml) were combined in a 20 ml scintillation vial,
sealed and heated to 115 oC for 48 h and cooled to room tem-
perature. The colorless polyhedral crystals were collected and
washed with DMF. The as-synthesized material was found to
be insoluble in H2O and common organic solvents. FT-IR
(4000−650 cm−1): 3485 (br), 2930 (w), 1651 (vs), 1495 (m),
1437 (m), 1386 (s), 1315 (w), 1253 (m), 1177 (w), 1093 (s),
1060 (w), 864 (w), 786 (m), 777 (m), 732 (m), 709 (m). Ele-
mental analysis found (calculated) for Tb6C80N12H84O43: C%:
31.8 (33.6), H%: 2.82 (2.97), N%: 5.96 (5.89).
AUTHOR INFORMATION
Corresponding Author
mohamed.eddaoudi@kaust.edu.sa
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENT
The authors gratefully acknowledge financial support from King
Abdullah University of Science and Technology (KAUST),
Kingdom of Saudi Arabia.
Synthesis of Tb-sph-MOF-2 (3). Tb(NO3)3·5H2O (8.3 mg,
0.0191 mmol), H3BTTC (2.5 mg, 0.0066 mmol), H3BTPB
(5.0 mg, 0.0075 mmol), 2-FBA (75.0 mg, 0.535 mmol), DMF
(1.5 ml) and H2O (1.0 ml) were combined in a 20 ml scintil-
lation vial, sealed and heated to 115 oC for 48 h and cooled to
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