Laboratory Experiment

pubs.acs.org/jchemeduc

Synthesis and Small Molecule Exchange Studies of a Magnesium

Bisformate Metal−Organic Framework: An Experiment in Host−
Guest Chemistry for the Undergraduate Laboratory
Jeffrey A. Rood*,† and Kenneth W. Henderson‡
†
Department of Chemistry and Biochemistry, Elizabethtown College, Elizabethtown, Pennsylvania 17022, United States
‡
Department of Chemistry and Biochemistry, University of Notre Dame, Notre Dame, Indiana 46556, United States
*
S Supporting Information

ABSTRACT: Experiments are described that introduce students to the important

concepts of host−guest chemistry and size exclusion in porous metal−organic frameworks
(MOFs). The experiment has been successfully carried out in both introductory and
advanced-level inorganic chemistry laboratories. Students synthesized the porous MOF, α-
Mg3(O2CH)6, and examined its ability to take up a variety of small organic molecules into
its pores using 1H NMR spectroscopy. The MOF exhibited size exclusion and students
rationalized this behavior based on the structures of the organic molecules and the pore
size of the MOF.

KEYWORDS: Separation Science, Solid State Chemistry, Materials Science, Second-Year Undergraduate,
Upper-Division Undergraduate, Inorganic Chemistry

R esearch into the design and synthesis of extended

materials with specific properties has received extensive
interest in recent times. Of the many classes of extended
materials, metal−organic frameworks (MOFs) have received
tremendous attention. MOFs are hybrid materials, composed of
metal ions and organic molecules that are linked into an
extended array by what is often referred to as a node-and-linker
approach. The most successful synthesis of these materials uses
metal−carboxylate systems.1 In many cases, metal carboxylates
form frameworks that enclatherate solvent molecules. In some
instances, these materials are robust to solvent removal,
generating a porous framework. The porous nature of many
MOFs makes them attractive for numerous applications
involving the uptake and exchange of small molecules.2
MOFs are ideal for such purposes as the size and shape of
the pores may be controlled through judicious choice of metal
ions and organic linker molecules.
Despite the high level of interest in MOF materials in the
academic setting, undergraduate students rarely receive
exposure to such cutting-edge applications of inorganic
chemistry. Recently, Sumida and Arnold published a MOF
laboratory designed for the undergraduate inorganic chemistry
laboratory that gives students excellent examples of synthesis
and characterization of such materials.3 The laboratory
experiment described herein provides an 1H NMR-based
study of the uptake properties of the MOF α-magnesium
formate, α-Mg3(O2CH)6.4 While students will gain experience
in the synthesis of MOF materials, the novelty of this
© XXXX American Chemical Society and
Division of Chemical Education, Inc.
experiment focuses on the host−guest chemistry of porous
materials. Host−guest studies have been the topic of a variety
of contributions to this Journal, yet none have focused
specifically on such properties in MOFs.5 As many institutions
do not have direct access to some of the instrumentation
common to MOF characterization, such as X-ray diffraction
and gas sorption equipment, this system uniquely provides a
straightforward investigation of small molecule uptake and size
selectivity of the MOF using NMR spectroscopy. Guest uptake
by the MOF can be determined by dissolving the material in
D2O and obtaining a 1H NMR spectrum.
Students that engaged in this experiment gained experience
in high-temperature synthesis and crystallization and learned
about the properties of extended materials. This experiment
was carried out in an introductory-level inorganic chemistry
course at Elizabethtown College over the past three years and
was completed by 82 students. Additionally, the experiment
was part of the laboratory curriculum for an advanced-level
laboratory course at the University of Notre Dame for five years
and was completed by 80 students. At Notre Dame, this
experiment was coupled with other solid-state experiments
dealing with zeolites6 and superconductors7 that have been
reported in this Journal, and elsewhere, as a unit on solid-state
chemistry. An introduction to MOF chemistry not only
provided students with exposure to a new area of inorganic
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Journal of Chemical Education
Scheme 1. Crystal Structures of α-Mg3(O2CH)6⊃DMF (left) and α-Mg3(O2CH)6 (right)a
a
The coordination environment around each magnesium center is shown as a yellow octahedron to help illustrate the pores within the material.
Hydrogen atoms have been omitted for clarity.
chemistry, but also allowed for broader discussion of important
topics related to MOFs, such as H2 storage8 and CO2
sequestration.9
■
EXPERIMENTAL OVERVIEW
This experiment utilized the smallest carboxylic acid, formic
acid, in the construction of the open framework α-
Mg3(O2CH)6 from a high-temperature reaction in dimethyl-
formamide (DMF). The decomposition of dialkylformamides
to compounds such as carbon monoxide, formic acid, and
dialkylamines helps drive the reaction toward the formation of
the MOF, allowing for a discussion of the reaction chemistry
with students.10 The crystallization of MOFs at elevated
temperatures was a new concept to most students, as typical
experiences in crystallization usually involve the cooling of
saturated solutions.
Completion of this laboratory exercise involved four steps
and was carried out over multiple class periods. Students first
synthesized α-Mg3(O2CH)6⊃DMF (the phase containing
DMF molecules in the pores) by the reaction of Mg-
(NO3)2·6H2O with 2 equiv of formic acid in DMF. The
reaction was carried out on a hot plate using a Teflon-capped
scintillation vial immersed in silicon oil bath at 110 °C.
Alternatively, an oven set to the desired temperature may be
used. Suitable quantities of crystalline product deposited on the
walls of the vial after 40 h. The material was stable in the
mother liquor until students were able to continue their studies.
Students isolated the crystalline product by vacuum filtration.
Typical yields ranged from 50 to 60% based on magnesium.
Second, 1H NMR was carried out on this sample in D2O. It is
important to note that although dissolving the material in D2O
destroys the integrity of the MOF, this method provides a
simple way for examining guest molecules that reside in the
pores. Because only a small quantity of solid is needed for the
NMR study, the majority of the solid material remained for
further studies regarding host−guest chemistry. From the 1H
spectrum of α-Mg3(O2CH)6⊃DMF, students were able to
identify the formate proton resonance along with the methyl
and formyl protons from DMF. An additional peak at δ2.4 was
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Laboratory Experiment
usually evident due to the presence of dimethylamine from the
decomposition of DMF.
Third, after isolating α-Mg3(O2CH)6⊃DMF, samples were
heated under reduced pressure at 130 °C using a vacuum pump
or vacuum oven. After 36 h, the guest-free, porous phase α-
Mg3(O2CH)6 was isolated. The crystal structures of α-
Mg3(O2CH)6⊃DMF and α-Mg3(O2CH)6 are shown in Scheme
1. Confirmation of the guest-free phase was evident in the 1H
NMR spectrum in D2O, where only the formate proton was
observed.
Fourth, students were tasked with investigating the solvent-
uptake properties of the porous phase and examining the
material for any selective uptake. This study focused on the
inclusion of THF, acetone, benzene, and cyclohexane; however,
many other compounds are suitable for investigation. Uptake
studies were carried out by soaking α-Mg3(O2CH)6 in each of
the pure solvents listed previously. Selectivity for guest
molecules was studied by soaking the MOF in a stoichiometric
mixture of the solvents under study. In all cases, the soaking
experiments were carried out between laboratory periods.
During the final laboratory session, students isolated the solids
by vacuum filtration and prepared 1H NMR samples of each
trial in D2O. Spectra were obtained for each uptake study,
which allowed students to determine whether any new guest
molecules where enclatherated into the MOF.
Over the course of the five years this experiment has been
run, the uptake studies were posed to students in one of two
ways. Originally, students were told directly how to investigate
the uptake properties of the MOF, as detailed in the Supporting
Information. Alternatively, and likely more challenging,
students were asked to develop 1H NMR experiments to
investigate small-molecule uptake of α-Mg3(O2CH)6 by only
being told that the MOF is soluble in D2O. This approach
forced students to think more critically about experimental
design and steered them away from the “cookbook” approach
to completing laboratory experiments.
■
HAZARDS
In all manipulations, students should wear standard personal
protective equipment, including safety goggles and gloves. The
Journal of Chemical Education
flammability of dimethylformamide, tetrahydrofuran, acetone,
benzene, and cyclohexane should be discussed with students
and these solvents should be handled in a fume hood.
Magnesium nitrate is an oxidizing agent and can cause eye
and skin irritation. Benzene is a carcinogen. When handling
benzene, all manipulations should be carried out in a fume
hood. This lab should only require ∼1 mL of benzene per
student. Formic acid can cause irritation or burns to the skin,
mucous membranes, and respiratory tract and should be
handled with care. Additionally, students should use caution
around hot silicon oil baths if used as the source of heat for the
experiment. In all cases, students should be encouraged to
consult MSDS sheets for all chemicals prior to beginning the
laboratory exercise.
■
RESULTS
Representative student 1H NMR spectra for this study are
shown in Figure 1. From the spectra, students were able to
Figure 1. Representative student-acquired 1H NMR spectra of α-
Mg3(O2CH)6⊃DMF, α-Mg3(O2CH)6, and each uptake experiment
described in this study. All spectra were obtained in D2O.
determine that THF, acetone, and benzene were taken up by α-
Mg3(O2CH)6, whereas cyclohexane was excluded, presumably
due to size. Furthermore, the spectrum resulting from soaking
the MOF in a stoichiometric mixture of the four solvents
showed preference for the uptake of acetone and THF over
benzene by comparing the integral ratios of these compounds.
Students were asked to consider reasons for the size selectivity
that is observed by thinking about both the guest molecule size
and the size of the pores in α-Mg3(O2CH)6. Students at Notre
Dame utilized Chem3D to compare guest molecule size. This
program was not available to all students at Elizabethtown and
more qualitative comparisons of Lewis structures proved
sufficient. Students investigated the crystal structures of α-
Mg3(O2CH)6 and its various inclusion compounds by down-
loading the crystallographic information files (.cif) from the
Cambridge Structural Database. Alternatively, the .cif files are
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Laboratory Experiment
available as Supporting Information in the original report of α-
Mg3(O2CH)6 in Inorganic Chemistry.4 Once students obtained
the .cif files, crude measurements of pore sizes were made using
software such as CrystalMaker or Mercury.
■ SUMMARY
This experiment provided a unique investigation of the host−
guest properties of MOFs and allowed such studies to be
carried out in a straightforward manner using 1H NMR
spectroscopy. The goals of this experiment included providing
students with experience in solid-state synthesis and, most
importantly, illustrating the important host−guest chemistry
that such materials exhibit. The latter served as a platform for
discussion of broader impacts of MOF materials in areas such
as alternative energy. Upon completion of the laboratory,
students wrote a formal report in which they carried out a
literature review of MOF chemistry in addition to reporting
their experimental findings and interpretations of the results
they observed. At both the introductory and upper-level course,
students found further examples of MOF applications in the
literature and were able to discuss their findings in context with
the experiment described here. Students found this experiment
to be interesting and enjoyable and many ranked it as their
favorite laboratory experiment in an informal end-of-semester
survey. Students also came to better appreciate the broader
applications of inorganic chemistry when MOFs and their
potential industrial and environmental uses were discussed. The
goals laid forth for this laboratory experiment were achieved in
that students were introduced to solid-state inorganic chemistry
and provided with examples of the numerous applications for
which such materials hold promise.
■
*
ASSOCIATED CONTENT
S Supporting Information
A student handout containing detailed experimental instruc-
tions for the synthesis of α-Mg3(O2CH)6 and the uptake
studies; details for instructors. This material is available via the
Internet at http://pubs.acs.org.
■ AUTHOR INFORMATION
Corresponding Author
*E-mail: roodj@etown.edu.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
We would like to thank students of Chemistry 443 at the
University of Notre Dame and Chemistry 242 at Elizabethtown
College for suggestions and helpful comments regarding the
design of this experiment. J.A.R. would like to thank the
National Science Foundation (grant CHE-0958425) for
instrument support.
■
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