SALE-Ing a MOF-Based “Ship of Theseus.” Sequential Building-Block Replacement for Complete Reformulation of a Pillared-Paddlewheel Metal-Organic Framework

Article abstract of DOI:10.1002/ejic.201600069

A complete structure and composition evolution of a pillared-paddlewheel metal-organic framework was achieved using a combination of solvent-assisted linker exchange (SALE) and node transmetalation. In this example, each building unit – the di-topic carboxylate strut, the di-topic nitrogen-based pillar, and the di-zinc node – of the original metal-organic framework is replaced in sequential fashion to produce a nickel-based daughter metal-organic framework with entirely different components.

Full text of DOI:10.1002/ejic.201600069

DOI: 10.1002/ejic.201600069
Communication
Post-Synthetic Transformation
SALE-Ing a MOF-Based “Ship of Theseus .” Sequential Building-
Block Replacement for Complete Reformulation of a Pillared-
Paddlewheel Metal-Organic Framework
[
a,b]
[a]
[a]
[a]
Yan Xu,
Nicolaas A. Vermeulen, Yangyang Liu, Joseph T. Hupp,* and
Omar K. Farha*[
a,c]
Abstract: A complete structure and composition evolution of lar, and the di-zinc node – of the original metal-organic frame-
a pillared-paddlewheel metal-organic framework was achieved work is replaced in sequential fashion to produce a nickel-based
using a combination of solvent-assisted linker exchange (SALE) daughter metal-organic framework with entirely different com-
and node transmetalation. In this example, each building unit ponents.
–
the di-topic carboxylate strut, the di-topic nitrogen-based pil-
Introduction
surface areas, with many exhibiting sufficient chemical versatil-
[
5]
ity to enable tailoring to a specific purpose. Among the most
extensively explored proof-of-concept purposes are gas storage
The Greek historian Plutarch, in Life of Theseus, asked whether
a decaying wooden ship that has been restored by gradually
replacing every component remains the same ship. Although
[6]
[7]
and release, heterogeneous condensed and gas-phase ca-
[
1]
talysis, chemical sensing, and drug delivery.[10] Most MOFs
[8]
[9]
[
2]
the simple answer would seem to be “no” the question does
point to the idea that an object is more than its constituent
parts. Through gradual component interchange the properties
of size and shape – both macroscopic and microscopic – may
be retained while constitution can be altered. For crystals of a
porous metal-organic framework (MOF), the retained properties
could also include topology and degree of network catenation,
while new properties such as catalytic functionality or increased
resistance to hydrolytic degradation may be introduced. An ex-
treme example would be gradual and stepwise replacement of
every component of a MOF – whether node, primary linker, or
secondary linker – with a related but chemically distinct compo-
nent, so as to yield a new porous crystalline MOF. For the sake
of illustration, and because of the increasing use of building-
are obtained through de novo syntheses, processes that can be
simplified, at least conceptually, to merely mixing the building
units together, with or without solvent, and allowing them to
self-assemble. Unfortunately, not all MOF topologies, spatial ar-
rangements, or building unit combinations are kinetically and/
or thermodynamically favored and attempts at de novo synthe-
sis can result in undesired topologies, framework catenation (in-
terpenetration or interweaving), or no framework at all.
To address these challenges post-synthesis modification/
[
5b,11]
elaboration methods,
and a successor concept – building-
block replacement (BBR) – have been developed. Broadly, BBR
encompasses strategies to: 1) replace the organic structural
components of a MOF though solvent-assisted linker exchange
(SALE), 2) replace nonstructural ligands, e.g. aqua or terminal
[
3]
block replacement (BBR) methods in MOF synthesis, we set
out to attempt such a transformation and obtain a MOF-based
analogue of the ship of Theseus.
hydroxo ligands, with desired functional ligands, a process that
[
12]
has been termed solvent-assisted ligand incorporation (SALI),
and 3) change the identities of metal components of a frame-
It is worth noting that MOFs have garnered tremendous at-
tention for their promise as highly tunable and potentially ro-
[13]
work by transmetalation. SALE entails the placement of MOF
crystals in a solution of “incoming” linkers where a dynamic
exchange, typically thermodynamically controlled via linker
concentration and/or Lewis basicity, and kinetically facilitated
by choice of solvent and reaction temperature, allows for the
systematic substitution of related linkers. Interestingly, the ex-
changing linkers need not be size matched. Through this proc-
ess, the pore volume, environment and aperture of a framework
can be modified while maintaining the topology of the original
framework. This strategy has proven effective in the construc-
tion of a variety of MOFs that have resisted to direct synthe-
[
4]
bust materials. MOFs have been shown to be capable of dis-
playing a variety of pore sizes and a broad range of internal
[
a] Department of Chemistry, Northwestern University,
145 Sheridan Road, Evanston, Illinois 60208, USA
2
E-mail: j-hupp@northwestern.edu
o-farha@northwestern.edu
http://chemgroups.northwestern.edu/hupp/
b] Department of Chemistry, College of Science, Northeastern University,
Shenyang 110819, P. R. China
c] Department of Chemistry, Faculty of Science, King Abdulaziz University,
Jeddah, Saudi Arabia
[
[
[
14]
sis.
change occurs via crystallite-to-crystallite transformation rather
Notably, for most examples reported to date, linker ex-
Supporting information for this article is available on the WWW under
http://dx.doi.org/10.1002/ejic.201600069.
[
15]
than by MOF particle dissolution and recrystallization.
Eur. J. Inorg. Chem. 0000, 0–0
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Communication
For node transmetalation most examples to date have like- linker being replaced. In the absence of backbonding the Bron-
wise involved site-by-site exchange of components within an sted basicity of the candidate linker is a good predictor of the
intact crystalline framework, rather than dissolution and recrys- relative metal-ligand bond strength and, therefore, the propen-
tallization with new components. MOF node transmetalation sity for SALE to occur. With this in mind, bpy pillars were re-
can endow a previously inert MOF with catalytic activity or placed with dabco pillars, where dabco is a superior Lewis base
redox activity. Or, it may serve to enhance gas adsorption prop- (Dabco = 4-diazabicyclo[2.2.2]octane). This step was accom-
erties or MOF chemical stability – especially if the metal ex- plished by soaking Zn (ndc) (bpy) in a DMF solution containing
2
2
change is followed by a change in metal oxidation state. Below 4-diazabicyclo[2.2.2]octane (dabco) (14 equiv.) to afford
we use two BBR methods, node transmetalation and SALE, and Zn (ndc) (dabco).
2
2
three BBR steps (SALE twice) to obtain a microporous crystalline
MOF possessing none of the original MOF building blocks.
Finally, Zn (tmbdc) (bpy) was converted (transmetalated) to
2
2
Ni (ndc) (dabco). It has been noted previously that for a limited
2
2
set of divalent transition metals, the Irving–Williams series is a
[
6c]
good predictor of success with transmetalation.
The series
Results and Discussion
correlates with relative strengths of coordination bonds and is
2
+
2+
2+
2+
ordered as follows: Cu > Ni > Co ≈ Zn . Thus, we expect
Our starting point was the known MOF, Zn (tmbdc) (bpy),
2
2
II
II
Ni to readily displace Zn , as indeed is observed here and else-
(
tmbdc = tetramethylterephthalate, bpy = 4,4′-dipyridyl); see
[
19]
II
[
16]
where.
Given the stronger bonding between Ni and both
Scheme 1.
Zn (tmbdc) (bpy) is an example of a non-cate-
2 2
carboxylate and nitrogen-presenting ligands, we anticipated
that SALE would likely be slower with nickel-containing nodes
than ones containing zinc. As such, we intentionally placed
transmetalation at the end of the transformation sequence; see
Scheme 1. to strengthen the metal-ligand interactions occur-
ring last. The most plausible route (see SI) from
nated pillared-paddlewheel MOFs. The pairs of zinc ions and
the paddlewheel-coordinated dicarboxylated linkers define the
2D sheets, while the axially ligated dipyridyl ligands serve as
pillars between the sheets. As shown in Scheme 1, the first SALE
step was carried out by placing 50 mg of Zn (tmbdc) (bpy) in
2
2
10 mL of a 1 M 2,6-naphthalenedicarboxylate (ndc) in DMF solu-
[
20]
Zn (tmbdc) (bpy) to Ni (ndc) (dabco)
through MOF inter-
2
2
2
2
tion. The mixture was then heated at 80 °C for 2 days and
1
change is thus 1) carboxylate strut exchange, 2) nitrogen pillar
exchange and 3) transmetalation from Zn to Ni (Scheme 1).
monitored by H NMR spectroscopy. The resultant daughter
framework, Zn (ndc) (bpy), showed complete exchange of the
2
2
tmbdc struts with ndc. {It should be noted that the resultant
Finally, transmetalation by iterative exposure (three times) of
Zn (ndc) (bpy) of the first SALE experiment is a new non-inter- Zn
(ndc) (dabco) to a concentrated solution of Ni(NO ) ·6H O
2
2
2
2
3
2
2
penetrated MOF that has not yet been reported. The MOF con- (8 equiv. with respect to Zn) in DMF (heated at 80 °C for 24 h)
structed from the same components obtained through de novo provided Ni1.5Zn0.5(ndc) (dabco). After 72 h, three cycles of ex-
2
[
17]
II
synthesis forms an interpenetrated structure, thus underscor- posure to Ni(NO ) , 73 % exchange of Zn for the more strongly
3 2
[
18]
II
ing the utility of SALE as a MOF synthesis tool.
}
coordinated Ni atoms were observed by inductively coupled
plasma-atomic emission spectroscopy (ICP-AES) (see Support-
ing Information).
1H NMR spectroscopic analysis of the digested frameworks
Zn (tmbdc) (bpy), Zn (ndc) (bpy), Zn (ndc) (dabco) and
2
2
2
2
2
2
Ni1.5Zn0.5(ndc) (dabco) (Figure 1) show the progressive trans-
2
formation from one framework to the other. Spectra of
the digested framework Zn (tmbdc) (bpy) (Figure 1, a) and
2
2
Zn (ndc) (bpy) (Figure 1, b) show complete exchange of the
2
2
tmbdc struts for the less sterically hindered ndc struts (tmbdc
pK = 2.89 and ndc pK = 3.69). Similarly, when comparing the
a
a
spectra (Figure 1, b and c) of digested Zn (ndc) (bpy) and
2
2
Zn (ndc) (dabco), complete replacement of the bpy pillars for
2
2
+
the “shorter” and more basic dabco pillars (bpyH pK = 4.33
and dabcoH pK = 8.7) is seen. In contrast, the H NMR spectra
a
+
1
a
(
(
Figure 1, c and d) of Zn (ndc) (dabco) and Ni1.5Zn0.5-
2 2
ndc) (dabco) show the same composition.
2
As the MOF crystals are not large enough for single crystal
analyses, the bulk phase purity of each MOF was established
by Powder X-ray Diffraction (PXRD). Figure 2 parallels the simu-
lated and experimental PXRD patterns for each MOF. The PXRD
Scheme 1. Representation of the parent framework with all of its original
components replaced completely with other new ones via SALE and trans-
metalation to give the daughter framework.
spectra of Zn (tmbdc) (bpy), Zn (ndc) (bpy) and Ni1.5Zn0.5
-
2
2
2
2
(
ndc) (dabco), as well as the isostructural Zn (ndc) (dabco), are
2
2
2
20]
[
in agreement with their simulated counterparts.
The hkl in-
SALE is most easily accomplished when the incoming linker dexed results for the main peaks of each material are also
has a higher affinity for the node-based metals than does the shown in Figure 2. Not surprisingly, in the PXRD patterns of
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2
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Communication
2
–1
2
–1
(
170 m g ) and Zn (ndc) (dabco) (230 m g ) are attributed
2 2
to partial collapse of the frameworks during activation. Even
when applying supercritical CO drying procedure to activate
2
this type of MOF topology, some lose of posorosity is observed.
2
–1
However, Ni1.5Zn0.5(ndc) (dabco) (820 m g ) benefits from an
2
enhancement in stability resulting from the exchange of the
II
II
[23]
Zn atoms for more strongly coordinating Ni atoms.
Conclusions
In summary, via sequential BBR steps we have observed conver-
sion of a de novo synthesized MOF to one containing com-
pletely different components – a ship of Theseus – but with
retention of the noncatenated pillared-paddlewheel motif, as
well as the crystallinity, of the initial material. Organic chemistry
promises almost infinite variability, by being able to envision
[
24]
numerous retrosynthetic routes
and string together any
number of functional group manipulations, ultimately leading
to the (admittedly hyperbolic) statement “we can make any-
thing .” When combined with conventional MOF synthesis tech-
niques, strategies such as PSM, with its many variants, building-
[
25]
Figure 1. Abbreviated 1H NMR spectra of the (a) Zn
Zn (ndc) (bpy), (c) Zn (ndc) (dabco) and (d) Ni1.5Zn0.5(ndc)
works digested with D SO in [D ]DMSO.
block replacement, liquid-phase epitaxy, and others are help-
ing to move MOF synthetic chemistry in the direction of this
ideal.
2
(tmbdc)
2
(bpy), (b)
2
2
2
2
2
(dabco) frame-
2
4
6
each framework studied, the peaks (labeled 001, 002, and 001)
corresponding to the planes between the pillar linkers shift to
higher 2θ values. This result indicates a reduction of distance
between the 2D sheets (Scheme 1). Most significant is that fol-
lowing complete replacement of each building block
Experimental Section
General: 1H NMR spectra were collected on a Bruker Avance III
500 MHz spectrometer. Inductively coupled plasma-optical emis-
sion spectroscopy (ICP-OES) was recorded on a Varian Vista-MDX
model ICP-OES spectrometer (Varian, Walnut Creek, CA) equipped
with a CCD detector and argon plasma to cover the 175–785 nm
spectral range. Powder X-ray diffraction patterns for capillary-en-
capsulated samples were obtained at room temperature with a
Bruker MX IμS microsource (Cu-Kα radiation) and ApexII CCD de-
tector. Samples were mounted in capillaries with supernatant liquid;
capillaries were sealed with wax and placed on goniometer heads
for mounting on the diffractometer. The PXRD data were collected
with an area detector as rotation frames over 180° in ꢀ at 2θ values
of 4° and 25° and exposed for 10 min for each frame. Powder-
pattern data were treated for amorphous background scatter. Prior
Ni1.5Zn0.5(ndc) (dabco) emerges as crystalline.
2
to the N adsorption experiments, MOFs were evacuated with su-
2
percritical CO in a Tousimis™ Samdri® PVT-30 critical point dryer. N
2
2
sorption isotherms were collected on an ASAP 2020 (Micromeritics).
CCDC 1034322 [for Ni (ndc) (dabco)] contains the supplementary
2
2
crystallographic data for this paper. These data can be obtained
free of charge from The Cambridge Crystallographic Data Centre.
Supporting Information (see footnote on the first page of this
article): Experimental details include the synthesis of tmbdc, MOF
synthesis, SALE and transmetalation conditions, H NMR, ICP, PXRD,
Figure 2. Simulated and experimentally obtained PXRD patterns of
1
Zn
2 2 2 2 2 2 2
(tmbdc) (bpy), Zn (ndc) (bpy), Zn (ndc) (dabco) and Ni1.5Zn0.5(ndc) -
and N adsorption for each MOF.
(
dabco).
2
N adsorption-desorption isotherms (see SI) were collected
on each material to determine porosity. Prior to N2 sorption
2
Acknowledgments
experiments, the materials were activated by supercritical CO
The authors thank Yongchul G. Chung for his contribution of
2
[
22]
drying.
(see Supporting Information) The adsorption experi- preparing a simulated structure of non-interpenetrated
ments yield BET surface areas for Zn (tmbdc) (bpy), Zn (ndc) (bpy). J. T. H. thanks David J. Hupp for introducing him
2
2
2
2
Zn (ndc) (bpy), Zn (ndc) (dabco) and Ni Zn0.5(ndc) (dabco) to the Theseus' Paradox. We gratefully acknowledge funding
2
2
2
2
1.5
–1
2
2
–1
2
–1
2
2
–1
are about 2000 m g , 170 m g , 230 m g and 820 m g , from the U. S. Dept. of Energy, Office of Science, Basic Energy
respectively. The low N2 surface areas for Zn (ndc) (bpy) Sciences Program through grant DE-FG02-08ER15967. Y. X. ac-
2
2
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3
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Communication
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Synthesis design · Carboxylate ligands · Coordination modes
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Received: January 26, 2016
Published Online: ■
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Communication
Post-Synthetic Transformation
Y. Xu, N. A. Vermeulen, Y. Liu,
J. T. Hupp,* O. K. Farha* .................. 1–6
SALE-Ing a MOF-Based “Ship of The-
seus.” Sequential Building-Block Re-
placement for Complete Reformula-
tion of
a
Pillared-Paddlewheel
Metal-Organic Framework
Text for Table of Contents: Interchange paddlewheel MOF has been achieved
of a non-interpenetrating Zn based pil- through the combination of solvent
lared-paddlewheel MOF into an en- assisted linker exchange and transmet-
tirely different Ni-based pillared- alation.
DOI: 10.1002/ejic.201600069
Eur. J. Inorg. Chem. 0000, 0–0
www.eurjic.org
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© 0000 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim