Aromatizing olefin metathesis by ligand isolation inside a metal- organic framework

Article abstract of DOI:10.1021/ja407333q

The aromatizing ring-closing metathesis has been shown to take place inside an extended porous framework. Employing a combination of solvent-assisted linker exchange and postsynthesis modification using olefin metathesis, the noninterpenetrated SALEM-14 was formed and converted catalytically into PAH-MOF-1 with polycyclic aromatic hydrocarbon (PAH) pillars. The metal-organic framework in SALEM-14 prevents "intermolecular" olefin metathesis from occurring between the pillars in the presence of the first generation Hoveyda-Grubbs catalyst, while favoring the production of a PAH, which can be released from the framework under acidic conditions in dimethylsulfoxide.

Full text of DOI:10.1021/ja407333q

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Communication
Aromatizing Olefin Metathesis by Ligand
Isolation Inside a Metal-Organic Framework
Nicolaas A. Vermeulen, Olga Karagiaridi, Amy A. Sarjeant, Charlotte
L. Stern, Joseph T. Hupp, Omar K. Farha, and J. Fraser Stoddart
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/ja407333q • Publication Date (Web): 18 Sep 2013
Downloaded from http://pubs.acs.org on September 20, 2013
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Nicolaas A. Vermeulen, Olga Karagiaridi, Amy A. Sarjeant, Charlotte L. Stern, Joseph T. Hupp, Omar
K. Farha, J. Fraser Stoddart
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Department of Chemistry, Northwestern University, 2145 Sheridan Road, Evanston, IL 60208, United States
Supporting Information Placeholder
starting materials containing vinyl benzene units. It is known19 as
ABSTRACT: The aromatizing ring-closing metathesis has been
the aromatizing ring closing metathesis (ARCM); its use inside
MOFs would enable the preparation of new extended frameworks
employing PSM and would permit the formation of exotic PAHs as
isolated linkers in MOFs.
shown to take place inside an extended porous framework. Em-
ploying a combination of solvent-assisted linker exchange and
post-synthesis modification using olefin metathesis, the non-inter-
penetrated SALEM-14 was formed and converted catalytically into
PAH-MOF-1 with polycyclic aromatic hydrocarbon pillars. The
metal-organic framework in SALEM-14 prevents “intermolecu-
lar” olefin metathesis from occurring between the pillars in the
presence of the first generation Hoveyda-Grubbs catalyst, while fa-
voring the production of a polycyclic aromatic hydrocarbon, which
can be released from the framework under acidic conditions in di-
methylsulfoxide.
Scheme 1. Use of Grubbs’ Catalyst to Make PAHs18b
Recently, metal-organic frameworks (MOFs) have attracted1 a lot
of attention as a unique class of highly adaptive nanoporous mate-
rials. The ability of MOFs to incorporate a wide variety of chemical
functionality, on account of their easily altered organic struts, has
resulted2 in their exploration for purposes such as gas storage3, gas
separation4, chemical sensing5, catalysis6, and drug delivery7. Alt-
hough de novo syntheses of MOFs with a range of different struts,
which facilitate the introduction of functionality, have been highly
successful, many metal/strut combinations react in quite unpredict-
able ways8 and lead to undesirable by-products. In order to over-
come these vagaries and achieve the formation of desired frame-
works, two alternative synthetic protocols have emerged: they are
(i) post-synthesis modification9 (PSM) and (ii) solvent-assisted
linker exchange10 (SALE). PSM refers to chemical modifications
of the organic struts in MOFs to either unmask11 reactive function-
ality or introduce12 functional groups which do not survive (or dis-
rupt) MOF synthesis and has become a common-or-garden ap-
proach to generate much sought-after extended frameworks. It is
worthy of note that few reports13 describe C–C bond-forming reac-
tions by PSM. By contrast, SALE allows for the exchange of struts
in readily obtainable MOFs to produce14 extended frameworks with
more chemically diverse and useful properties. These two funda-
mentally different protocols are not mutually exclusive and, em-
ployed in concert, can be used to generate metal/strut combinations
in MOFs that are not attainable by any other means.
In order to aid and abet the efficient and rapid synthesis of large-
pore, non-interpenetrated frameworks containing PAHs, we turned
our attention to SALE methodology.10 We employed the preformed
non-interpenetrated framework20 Br-YOMOF which is con-
structed (Scheme 2) from Zn(NO3)2 and two organic components –
(1) the tetracarboxylic acid ligand 1 (with two bromine atoms21 on
the central phenylene ring to block interpenetration) which forms
2D sheets with Zn2+ dimers and (2) the dipyridyl strut 2 which links
the 2D sheets by coordinating to the zinc paddlewheel clusters
forming perpendicular pillars separating the 2D layers. Following
the synthesis of Br-YOMOF, the pillars can be exchanged for dif-
ferent dipyridyl linkers employing SALE to provide access to a
non-interpenetrated framework without having to resort to de novo
synthesis.
Scheme 2. Synthesis of Non-Interpenetrated Br-YOMOF
The ability of the olefin metathesis popularized by the extensive
use15 of Grubbs’ catalysts16, to transform molecular structure is
both unique and chemically enabling17. In addition to the extensive
use of this reaction in the fields of polymer chemistry15b and mate-
rials science15b, olefin metathesis has been employed in the synthe-
sis of numerous complex small-molecule compounds15a. One ex-
ample18 of this ubiquitous structural transformation is the genera-
tion (Scheme 1) of polycyclic aromatic hydrocarbons (PAHs) from
One of the major benefits of doing chemistry inside a highly or-
ganized porous material is the unique ability of a rigid, extended
framework to site-isolate reactive functional groups and thus pre-
vent unproductive “intermolecular” chemistry. In order to test this
concept, we elected to make a strut, which does not, on its own,
undergo intramolecular ring-closing metathesis, but instead only
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Scheme 3. Synthesis of SALEM-13 and Olefin Metathesis of 3 and SALEM-13
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Figure 1. (a) Experimental PXRD of Br-YOMOF, (b) experimental PXRD of SALEM-13 as synthesized, (c) calculated PXRD of SALEM-13, and (d)
experimental PXRD of SALEM-13 after olefin metathesis. The partial 1H NMR spectra of (e) the divinyldipyridyl linker 3, (f) the tetracarboxylic acid ligand
1, (g) regenerated22 products (1 and 3) from SALEM-13, (h) regenerated22 products (1 and 3), following treatment (120C / 48 h) of SALEM-13 in DCE with
the first generation Hoveyda-Grubbs catalyst, (i) the crude reaction mixture, following treatment (120C / 24 h) of 3 in DCE with the first generation Hoveyda-
Grubbs catalyst. All spectra were recorded in CD3SOCD3 containing a few drops of D2SO4 at 298 K on a 500 MHz spectrometer.
produces poorly defined polymeric material when exposed to an
olefin metathesis catalyst. The divinylpyridyl linker 3 was prepared
(see Supplementary Information) and subjected to SALE in order
to produce (Scheme 3, Figure 1a,b) SALEM-13. The powder X-
ray diffraction (PXRD) pattern of SALEM-13 confirms (Figure
1b) its crystallinity. Furthermore, after the unit cell had been in-
dexed, it was evident that a reduction in its size had taken place
during the SALE performed on Br-YOMOF to afford SALEM-
13. The observed [001] peak in Br-YOMOF and SALEM-13 cor-
responds to a reflection originating from the c-axis direction along
which the dipyridyl pillars lie. The shift from 2θ = 3.94 (Figure 1b)
in Br-YOMOF to 2θ = 4.80 (Figure 1a) in SALEM-13 points to the
incorporation of a shorter pillar.23
The pyridyl portions of 6 were prepared in two steps from 4-chlo-
ropyridine. Its thermodynamic deprotonation using lithium diiso-
propylamide (LDA), followed by quenching with ethyl formate be-
fore carrying out a Wittig reaction with MePPh3Br produced24 the
desired intermediate 4 in 21% over the two steps (Scheme 4). 1,4-
Dibromo-2,5-dimethylbenzene was further brominated (NBS,
C6H6), affording 1,4-dibromo-2,5-bis(bromomethyl)benzene
which was treated with PPh3 to generate the diphosphonium bro-
mide before reacting it with paraformaldehyde to give 1,4-di-
bromo-2,5-divinylbenzene. A subsequent Miyaura borylation af-
forded25 the intermediate 5 in 34% yield over the three steps. The
tetravinyldipyridyl strut 6 was obtained in 53% yield as a result of
carrying out a Suzuki coupling between 4 and 5 using palladium
(π-allylchloride)tri(tert-butyl)phosphine) as the catalyst26. We at-
tempted to prepare (Scheme 5) the PAH 7 in DCE at 120 °C, using
In a dichloroethane (DCE) solution, exposure of 3 to the first
generation Hoveyda-Grubbs (HG) catalyst at 120 °C leads to the
formation (Scheme 3) of the expected polymeric product as indi-
cated by the broad resonances (Figure 1i) in its 1H NMR spectrum.
By contrast, the two vinyl groups in the pillars of the porous ex-
tended framework provided by SALEM-13 revealed no reactivity
at all (Figure 1e-h), even after prolonged exposure to the same HG
catalyst under identical conditions. This observation is consistent
with the hypothesis that the MOF site-isolates the potentially reac-
tive olefins, preventing them from undergoing “intermolecular”
metathesis. In this knowledge, we undertook the preparation
(Scheme 4) of the tetravinyldipyridyl strut 6 which, in principle,
should be able to undergo ARCM.
Scheme 4. Synthesis of the Tetravinyldipyridyl Strut 6
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Scheme 5. Synthesis of SALEM-14 and Olefin Metathesis of 6 and SALEM-14
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Figure 2. (a) Experimental PXRD of Br-YOMOF, (b) experimental PXRD of SALEM-14 as synthesized, (c) calculated PXRD of SALEM-14, and (d)
experimental PXRD of PAH-MOF-1 after ARCM. The partial 1H NMR spectra of (e) the tetravinyldipyridyl linker 6 in CDCl3, (f) the crude reaction mixture
from the homogeneous ARCM of 6 following treatment (120C / 24 h) with the first generation Hoveyda-Grubbs catalyst in CDCl3, showing some broadening
of the resonances as a result of some intermolecular polymerization, (g) the tetravinyldipyridyl linker 6 in CD3SOCD3 / D2SO4, (h) the tetracarboxylic acid
ligand 1 in CD3SOCD3 / D2SO4, (i) regenerated22 products (1 and 6) from SALEM-14 dissolved in CD3SOCD3 / D2SO4 and, (j) regenerated22 products (1 and
7) from PAH-MOF-1 dissolved in CD3SOCD3 / D2SO4, following treatment (120C / 48 h) of SALEM-14 in DCE with the first generation Hoveyda-Grubbs
catalyst. All spectra were recorded at 298 K on a 500 MHz spectrometer.
the first generation HG catalyst. The result was only insoluble pol-
ymeric material: no 7 could be detected in the reaction mixture.
This outcome was hardly surprising as the intermolecular poly-
ermization could be favored under these conditions. It should be
noted that ruthenium catalysts employed in metathesis may be poi-
soned by soft donors, including pyridine.27 If, however, the tetra-
vinyldipyridyl strut is converted into the pillars of a MOF, then the
pyridyl nitrogen atoms in 6 will become strongly coordinated to the
dinuclear Zn2+ nodes and so will be unable to interfere with the
ARCM. Moreover, the extended structure of the MOF prevents the
undesired polymerization between tetravinyldipyridyl pillars
which characterizes the reaction of 6 in solution.
HG catalyst in DCE at 120 °C (Figure 2g-j). Within one day, a sig-
nificant amount of the tetravinyldipyridyl strut 6 had been con-
verted into the PAH strut 7, as demonstrated by the 1H NMR spec-
troscopic monitoring procedure22. At the end of the second day, 6
had been converted completely into 7 (Figure 2j) inside the ex-
tended structure. By contrast, the much larger29 first generation
Grubbs’ catalyst was totally ineffective in converting the divinyldi-
pyridyl pillars in SALEM-14 into the PAH pillars in PAH-MOF-
1 – that is, the mismatch between the size of a catalyst and the di-
mensions of the pores of a MOF can prevent catalysis from occur-
ring.
In summary, we have demonstrated the use of a suitably-sized
ruthenium-based olefin metathesis catalyst inside a metal-organic
framework to carry out a solid-state reaction in a post-synthetic
fashion that cannot be accomplished in the solution phase. This
proof-of-concept investigation, not only demonstrates the synthetic
potential of combining post-synthetic modifications with solvent-
assisted linker exchange inside the metal-organic framework
toolbox, but also establishes the feasibility of performing “intramo-
lecular” chemical transformations where the substrates are pre-
vented from undergoing “intermolecular” reactions in robust, po-
rous extended frameworks. It is clear that these frameworks are ca-
pable of exercising size selectivity towards catalysts and presuma-
bly also reagents. This kind of solid-state reaction engineering
Thus, employing SALE, strut 6 was incorporated into the Br-
YOMOF architecture, resulting (Scheme 5, Figure 2a,b) in the pro-
duction of SALEM-14 with near quantitative conversion. The
SALE reaction was monitored22 by 1H NMR spectroscopy to en-
sure complete exchange of the precursor ligand and the new ex-
tended structure was analyzed (Figure 2b) by PXRD and shown28
to be SALEM-14, an outcome which was confirmed (see the SI)
by single-crystal X-ray structural analysis. SALEM-14 was rinsed
thoroughly with degassed DCE by soaking the crystals in the sol-
vent for 48 h, replacing the solvent every 12 h in order to remove
any DMF remaining from the SALE reaction. The formation of the
PAH 7 was achieved (Scheme 5) by PSM employing ARCM on the
extended porous structure of SALEM-14 with the first generation
3
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Complete experimental of new compounds and crystallographic
data of the prepared MOFs including CIF files. The Supporting
InfThis information is available free of charge via the Internet at
http://pubs.acs.org.
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Stoddart@northwestern.edu
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The authors declare no competing financial interest.
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(21) Although this compound contains some of the mono-Br-mono-NO2
derivative, it still leads to the formation of the non-interpenetrated MOF.
(22) Crystals isolated from the reaction were washed with DCE, dried,
suspended in CD3SOCD3 and dissolved using a few drops of D2SO4. This
procedure destroys the framework and allows the characterization of its
constituents by 1H NMR spectroscopy.
(23) Starting form the divinyldipyridyl linker 3 or the tetravinyldipyridyl
linker 6, direct attempts to synthesize SALEM-13 or SALEM-14, respec-
tively, were not successful, validating the SALE approach.
(24) The 4-chloro-3-vinylpyridine intermediate was purified by silica gel
plug filtration and carried forward without further purification. This inter-
mediate is volatile and purification simply results in loss of product.
(25) It should be noted that the yield (50%) for the Miyaura borylation
is low because of technical issues that had to be confronted during purifica-
tion of the product. Silica gel chromatography with 0—5% EtOAc/hexanes
was not efficient and the product had to be crystallized from hot hexanes.
(26) This catalyst was found to be the most reliable at producing product.
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catalyst, reactivity can be impaired. See: (a) Slugovc, C.; Demel, S.; Stelzer,
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(28) In comparison with the structural transformation from Br-YOMOF
to SALEM-13 where 2θ = 3.94 (Figure 1a/b), 2θ = 4.76 (Figure 2a/b) on
going from Br-YOMOF to SALEM-14, indicating the incorporation of a
shorter pillar, an observation which is in good agreement with the predicted
PXRD spectrum (Figure 2c).
The authors thank our joint collaborators Dr. Turki S. Al-Saud and
Dr. Nezar H. Khdary from the King Abdulaziz City of Science and
Technology (KACST) in Saudi Arabia for their interest in this re-
search program. O.K., J.T.H., and O.K.F. gratefully acknowledge
financial support from U.S. Dept. of Energy, Office of Science,
Basic Energy Sciences program (grant no. DE-FG02-08ER15967).
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(29) Marvin was used for analyzing the relative size of the Grubbs' cata-
lysts, Marvin 6.0.2, 2013, ChemAxon (http://www.chemaxon.com): Mini-
mum projection radius was calculated to be: HG1 (6.15 Å) < HG2 (6.68 Å)
< G2 (7.50 Å) < G1 (7.89 Å).
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