Anion-cation mediated structural rearrangement of an in-derived three-dimensional interpenetrated metal-organic framework

Article abstract of DOI:10.1021/acs.inorgchem.6b02584

Postsynthetic modification of metal-organic frameworks (MOFs) has proven an effective method of synthesizing architectures that have proven challenging to produce via classic solvothermal means. Herein we report the anion-cation assisted solid-state trans

Full text of DOI:10.1021/acs.inorgchem.6b02584

Article
pubs.acs.org/IC
Anion−Cation Mediated Structural Rearrangement of an In-derived
Three-Dimensional Interpenetrated Metal−Organic Framework
Michael K. Bellas,†,§ Joseph J. Mihaly,†,§ Matthias Zeller,‡ and Douglas T Genna*,†
†Department of Chemistry, Youngstown State University, Youngstown, Ohio 44555, United States
‡Department of Chemistry, Purdue University, West Lafeyette, Indiana 47907, United States
S
* Supporting Information
ABSTRACT: Postsynthetic modification of metal−organic frameworks (MOFs) has proven an effective method of synthesizing
architectures that have proven challenging to produce via classic solvothermal means. Herein we report the anion−cation assisted
solid-state transformation of a three-dimensional MOF (ATF-1) to a series of two-dimensional structures (YCM-21-Z) via
treatment with quaternary ammonium halides. It is important to note that this reaction requires no exogoneous building blocks
(inorganic cation and/or organic linker) for conversion to occur. This reaction led to the synthesis of a chemically unique
framework YCM-21-Bnpy in which phase-pure synthesis cannot be achieved by solvothermal means. The mechanism of
transformation was studied with data supporting a nucleophilic halide (Br, Cl, or F) mediated de-intercalation and cation-assisted
flattening of the In secondary building unit as the key mechanistic steps.
Recently we reported a series of new solvothermally
synthesized two-dimensional (2D) anionic MOFs (YCM-21-
Z) derived from 2,5-thiophenedicarboxylic acid containing an
[In(CO2R)4]− SBU.12 It is noteworthy that the anionic
framework of the YCM-21 series is chemically identical to
that of the three-dimensional (3D) interpenetrated MOF ATF-
1 also derived from 2,5-thiophenedicarboxylic acid and
containing an [In(CO2R)4]− SBU.13 The only chemical
difference between these two structures is the resident
charge-balancing quaternary ammonium cations for YCM-21
INTRODUCTION
■
Metal−organic frameworks (MOFs) are a synthetically diverse
class of materials with an equally diverse set of applications
focused on small-molecule storage and separation, catalysis,
drug delivery, and others.1 Traditional MOF synthesis
(solvothermal synthesis, template-induced synthesis, etc.) relies
on the self-assembly of inorganic and organic building blocks to
form a supramolecular structure.2 Transformations on existing
MOF scaffolds (i.e., post-synthetic modifications (PSM)) have
largely focused on nonarchitecture altering ligand functionaliza-
tion reactions;3 however, PSM that yield architecturally unique
frameworks from the parent structure are comparatively
sparse.4 Currently there are two prevailing modes of action in
supramolecular structure altering PSM. The first method
involves treating a presynthesized MOF with a new organic
linker, allowing for linker-exchange reactions to occur yielding
either an isoreticular structure5,6 or a structurally rearranged
MOF (Figure 1A).7 A second complementary approach
involves treating a presynthesized MOF with new inorganic
building blocks to either transmetalate the existing secondary
building unit (SBU) yielding an isoreticular structure6,8,9 or to
construct an entirely new SBU yielding a structurally rearranged
MOF (Figure 1B).10 Neither of these approaches synthesizes
the new MOF via rearrangement of the original building units.
However, Chen has recently reported a reversible solvent-
mediated de-interpenetration of a Zn-derived framework.11
+
and Me2NH2 for ATF-1. We hypothesized that due to their
chemical similarity the two frameworks may be interconvertible
under appropriate cation exchange conditions (Figure 2).
Herein we report a complementary strategy to existing
framework altering PSM methods via synergistic anion−cation
induced framework rearrangement reaction in which no
exogenous framework building unit is present to induce
transformation.
EXPERIMENTAL SECTION
■
General Procedure for Treatment of ATF-1 with Ammonium
Bromide at Room Temperature. To a 4 mL vial with a Teflon cap
was added 25 mg of activated ATF-1 (see Supporting Information for
activation protocol), 1.5 mL of DMF, and 1.5 mL of a 0.32 M solution
Received: October 26, 2016
© XXXX American Chemical Society
A
DOI: 10.1021/acs.inorgchem.6b02584
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Figure 1. (a) PSM via linker exchange with architectural transformation (blue) and without (orange). (b) PSM via nodal exchange with architectural
rearrangement (blue) and without (orange).
Figure 2. Proposed cation-induced architectural rearrangement.
Scheme 1. Conversion of ATF-1 to YCM-21-TEA
of the appropriate ammonium bromide (0.48 mmol) in CH2Cl2. The
RESULTS AND DISCUSSION
■
vial was then allowed to agitate on an orbital shaker at room
Initial efforts began by treating a DMF suspension of ATF-1
with a 0.08 M solution of tetraethylammonium bromide
temperature for 14 d. The vial was then removed from the shaker, and
all liquids were decanted off. The remaining solid was then washed
with fresh dimethylformamide (DMF; 3 × 3 mL), and a powder X-ray
(TEABr) in dichloromethane at room temperature. After one
week, partial conversion of ATF-1 to previously reported YCM-
21-TEA (Scheme 1) was observed using PXRD (Figure 3). The
reaction could be driven to full conversion in one week by
increasing the TEABr concentration of the solution to 0.16M.
The effectiveness of the architectural rearrangement was
optimized by exploring the reaction outcome as a function of
the counteranion of the [Et4N]+X− salts used. However, of the
commercially available tetraethylammonium salts screened, the
only one soluble in dichloromethane was TEABr. This lack of
solubility was overcome by performing the reactions in DMF
(results summarized in Table 1). Treatment of ATF-1 with
DMF solutions of TEACl and TEAF yielded YCM-21-TEA
diffraction (PXRD) pattern was then obtained immediately after.
General Procedure for Treatment of ATF-1 with Ammonium
Bromide at 120 °C. To a 4 mL vial with a Teflon screw cap was
added 25 mg of activated ATF-1(see Supporting Information for
activation protocol), and 3 mL of a 0.16 M solution of the appropriate
ammonium bromide (0.48 mmol) in DMF. The vial was then placed
in an oven held at 120 °C for 24 h. The vial was then removed from
the oven, and all liquids were decanted off without cooling to room
temperature. The remaining solid was then washed with fresh DMF (3
× 3 mL), and a PXRD pattern was then obtained immediately after.
B
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Figure 3. PXRD patterns of ATF-1, YCM-21-TEA, and ATF-1 soaked in 0.08 and 0.16 M solution of TEABr for one week. Note red and blue
dotted guidelines have been added for intense ATF-1 and YCM-21-TEA peaks.
−
−
BF4 , TfO−, and NO3 were not competent in facilitating this
reaction at room temperature. Strikingly, when run in DMF
TEABr no longer facilitates this reaction. Reactivity could be
restored by adding as little as 1 equiv (to cation) of
dichloromethane; however, for complete conversion 49 equiv
were required (Figure S6). We attribute the recovery of
reactivity of TEABr in DMF/CH2Cl2 to the presence of trace
chloride anions in CH2Cl2 under the reaction conditions. Free
chloride may be formed by nucleophilic attack of bromide on
dichloromethane to yield free chloride and bromochloro-
methane via a Finkelstein reaction.14
Variable-temperature studies revealed that when ATF-1 was
suspended in 0.16 M solutions of either TEACl in DMF or
TEABr in DMF/CH2Cl2 (1:1 by volume) at 120 °C,
dissolution of the framework was observed within 24 h, rather
than conversion into YCM-21-TEA. Dissolution was attributed
to the presence of large amounts of chloride at high
Table 1. Effect of Counter Anion on Reaction Conversion
X
outcome
F
complete conversion
complete conversion
no reaction
Cl
Br
Br
a
complete conversion
no reaction
BF4
NO3
OTf
no reaction
no reaction
a
With 49 equiv of CH2Cl2.
quantitatively after one week. DMF solutions containing
ammonium salts with non-nucleophilic counteranions such as
Figure 4. Substrate scope.
C
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Figure 5. (a) YCM-21-Bnpy, (b) YCM-21-Bnpy with A (purple)B (orange) layers color-coded, (c) single node of YCM-21-Bnpy, (d) side view of
YCM-21-Bnpy with A (purple)B (orange) layers color-coded. Note cations and solvent molecules were removed for clarity.
Scheme 2. Proposed Reaction Mechanism
temperature leading to the synthesis of soluble InCl3 and
[InCl4]− as we found ATF-1 solubilized under these conditions
even in the absence of exogenous ammonium salt. However, if
ATF-1 was treated with a 0.16 M solution of TEABr in DMF
complete conversion to YCM-21-TEA was observed after 24 h
at 120 °C. Notably the same reaction under ambient conditions
showed no signs of transformation (Table 1). Additionally the
solid-state transformation will occur at temperatures as low as
80 °C in DMF; however, 120 °C yielded the cleanest
transformations across all cations studied (vide infra).
Energy-dispersive X-ray spectroscopy (EDS) of YCM-21-
TEA synthesized via solid-state conversion of ATF-1 revealed
trace amounts of Br or Cl dependent on which TEA salt was
used during synthesis (Figures S11 & S12). Observed chloride
levels were below the amount found in YCM-21-TEA
synthesized under traditional solvothermal conditions. Impor-
tantly, the ATF-1 used in these experiments contained no
observable Cl, indicating that all endogenous halide present in
YCM-21 formed under the solid-state transformation con-
ditions can be completely attributed to R4NX. 1H NMR
D
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analysis of digested solid-state synthesized YCM-21-TEA
at high temperature the use of chloride and fluoride lead to
dissolution most likely via additional attacks of halide on
indium yielding soluble InXn species. It is posited that the role
of the cation influences the shift from a 3D framework to a 2D
framework, namely, via cation−π interaction between the
thiophene linker and ammonium cation. This is consistent with
our previous findings, which demonstrated that quaternary
ammonium cations participate in cation−π interactions in 2D
frameworks allowing for the formation of pseudosquare planar
In centers.12 The synergism between the cation and anion of
the reacting ammonium salts was further supported when ATF-
1 was treated with a DMF solution of NH2Me2Cl (at room
temperature) and NH2Me2Br (at 120 °C), respectively, yielding
only unreacted ATF-1 and no 3D deintercalated material. This
finding suggests that cation exchange must happen prior to or
during the de-interpenetration event; otherwise, the carboxylate
rebound will simply reform the starting framework. Although a
partial dissolution-recrystallization mechanism cannot be
formally ruled out in lieu of a formal solid-state to solid-state
transformation, inspection of the material post solid-state
transformation via optical microscopy (Figure S7) indicates
similar crystal habit, albeit with a decrease in overall
crystallinity. The transformed crystals retain their shape but
become opaque and are transformed into multicrystalline
agglomerates, as evidenced by single-crystal XRD attempts.
Lastly it is worth noting that the conversion to the 2D
framework is irreversible. Treatment of YCM-21-TEA with any
ammonium cation fails to yield any reaction. We have
previously attributed this to the relative small aperture size of
the YCM-21 series, prohibiting the removal of any endogenous
cation.
+
indicated exchange of the Me2NH2 cation endogenous to
ATF-1 for Et4N+ (Figures S13−S16). In concert, the EDS and
NMR experiments support the synergistic role of the cation−
anion pair (vide infra).
Treatment of ATF-1 with 0.16 M DMF solutions of spMPBr
and TEBABr at 120 °C, respectively, led to complete
conversion, as determined by PXRD, to the respective 2D
structure (Figure 4). Although treatment with spPPBr in DMF
at 120 °C led to complete consumption of ATF-1, the resulting
material was a phase impure mixture as determined by PXRD.
This phase impure mixture is posited to be a combination of
polymorphs of YCM-21-spPP. This is consistent with our
previous observation that YCM-21-TEBA can be formed in
both an ABAB and ABA′B′ layered structure.12 It was found
that spMPCl and spPPCl did induce the reaction in DMF at
room temperature; however, reaction times of 10 d were
necessary for full conversion. Exposure of ATF-1 to a DMF
solution of N-butyl-2,6-lutidinium bromide or any protic
ammonium cation (N-butylpiperidinium bromide, dimethylam-
monium bromide) at 120 °C yielded only unreacted ATF-1.
Treatment of ATF-1 with a DMF solution of N-
benzylpyridinium bromide(BnpyBr) at 120 °C yielded a new
framework, YCM-21-Bnpy. Attempts to grow this framework
under solvothermal conditions yielded a mixture of ATF-1 with
only trace amounts of YCM-21-Bnpy present. PXRD analysis of
bulk samples resulting from attempts at solvothermal synthesis
of YCM-21-Bnpy indicated the presence of only ATF-1.
However, close examination of the crystal crop using optical
microscopy revealed <5% of a new phase of material (Figure
S8). Single-crystal X-ray analysis proved these isolated crystals
to be identical to polycrystalline YCM-21-Bnpy synthesized via
cation exchange. Efforts to optimize solvothermal synthesis
conditions for phase-pure YCM-21-Bnpy were unsuccessful and
typically decreased the amount of YCM-21-Bnpy present,
yielding phase-pure ATF-1. YCM-21-Bnpy, shown in Figure 5,
is a 2D framework with an ABAB repeating pattern with the
largest pore apertures in the YCM-21 series (7.6 Å × 7.6 Å)
and is isotypic to the other members of the series. This result
demonstrates that this solid-state conversion protocol can be
utilized to access frameworks that are otherwise not accessible
through traditional solvothermal routes.
In summary, a new complementary mechanistic pathway for
the solid-state architectural rearrangement of MOFs has been
reported via synergistic anion−cation activation. Initial anionic
attack on an indium center of a 3D interpenetrated MOF
followed by cation-assisted structural rearrangement and
“flattening” of the framework yielded previously reported 2D
non-interpenetrated architectures. The applicability of the
structural rearrangement protocol is being examined with
other In-derived frameworks and non-In-derived SBUs. Our
efforts in these areas will be reported when appropriate.
ASSOCIATED CONTENT
To account for all of these observations we propose the
following mechanism for the transformation of ATF-1 to YCM-
21-Z (Scheme 2). Reversible nucleophilic attack by the
counteranion (Cl− or F− or Br− at high temperatures) leads
to temporary cleavage of one of the In carboxylate bonds of the
SBU forming a transient [In(CO2R)3X]− node. The framework
containing the new halogenated SBU can then de-inter-
penetrate from the host framework following cation exchange,
after which carboxylate rebound can occur displacing the
halogen, leaving behind a partially de-interpenetrated frame-
work. This series of elementary steps repeats until the two
formerly interpenetrating frameworks are entirely separate, at
which time the independent frameworks “flatten” to form the
2D structure.
■
S
* Supporting Information
The Supporting Information is available free of charge on the
ACS Publications website at DOI: 10.1021/acs.inorg-
chem.6b02584.
Additional experimental procedures and characterization
data (PXRD, EDS, and optical microscopy) (PDF)
X-ray crystallographic information (CIF)
AUTHOR INFORMATION
■
Corresponding Author
*E-mail: dtgenna@ysu.edu.
The temperature-dependent competency of bromide in this
reaction is worth comment. We hypothesize that at low
temperature the rate of the reverse reaction (k−1) of initial
halide attack is faster than the following cation exchange (k2).
Heating the reaction could result in an increased rate of
diffusion of the quaternary ammonium cation leading to an
increase in k2, driving the reaction to completion. Additionally,
ORCID
Douglas T Genna: 0000-0002-2407-8262
Author Contributions
§M.K.B. and J.J.M. contributed equally. The manuscript was
written through contributions of all authors. All authors have
given approval to the final version of the manuscript.
E
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Funding
We thank YSU Chemistry Department, STEM College, and
Graduate School for start-up funds. The X-ray diffractometers
were funded by NSF Grant No. DMR 1337296.
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
■
We gratefully acknowledge the Materials Research Laboratories
Inc. of Youngstown, OH, for graciously allowing us use of their
EDS Facility.
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