Unique structural micro-adjustments in a new benzothiadiazole-derived Zn(II) metal organic framework: Via simple photochemical decarboxylation

Article abstract of DOI:10.1039/c7cc06125k

The first example of micro-adjustments of a metal organic framework (MOF) structure was observed in a new Zn(ii) MOF (Zn-BTDC-M1) derived from a benzothiadiazole-4,7-dicarboxylic acid (H₂BTDC) ligand using a light-driven decarboxylation process. Interestingly, such decarboxylation occurs at the non-chelated wing of the ligand, which induced a change in the capability of the MOF for physical N₂ adsorption and chemical NH₃ gas adsorption.

Full text of DOI:10.1039/c7cc06125k

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Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc
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N@C2n (2n
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Unique structural micro-adjustment in a new benzothiadiazole-
derived Zn(II) metal organic framework by simple photochemical
decarboxylation
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
Xiao Han, Qing Cheng, Xiangru Meng, Zhichao Shao, Ke Ma, Donghui Wei, Jie Ding*, Hongwei
Hou*
www.rsc.org/
The first example of micro-adjustment of MOF strucutre was photochemical reaction can be used as an attractive strategy
observed in new Zn(II) metal organic framework (MOF) derived for micro-adjustment of MOF structure to modulate its
2
from benzothiadiazole-4,7-dicarboxylic acid (H BTDC) ligand (Zn- function. As we know, photochemical reaction based on
BTDC-M1), by light-driven decarboxylation process. Interestingly, electron transfer or energy transfer was usually fast and hardly
such decarboxylation occurs at the non-chelated wing of ligand, controllable in solution, whereas in the suitable restricted
which induces the changed capability of physical N
and chemical NH gas adsorption.
2
adsorption media, the yield of selected product would be remarkably
1
5
16,17
3
enhanced,
such as photochemical decarboxylation.
1
8
Recently, except for metal ion signaling in biology, photo-
induced decarboxylation is also very useful for solid state
During the this decade, optical-functional metal-organic
frameworks (MOFs) system, have shown the very attractive
1
9
actinometry. Hence, in chromophore-derived MOF scaffold,
this new strategy might be praticed to adjust the micro-
structure of parent MOF.
1
-4
application prospect in different areas, including sensor,
nonlinear optics, light-emitting technology, light-harvester and
photocatalysis. Since that, constructing suitable MOFs to
explore the excellent optical-functional material is always one
interesting and noteworthy research. One important synthetic
strategy is the modulation of centre metal ion in such system,
As well-known, the ligand terephthalic acid is a super linker
to construct many MOFs, including the famous pioneer MOF-
2
.
0
5
However, the structural character of terephthalic acid
might hinder its direct application in optical-functional
material. Herein, one analogue of terephthalic acid,
1
c,5
typically in lanthanide-MOF (Ln-MOF) material.
However,
the developments of relatively various transition metal ions in
benzothiadiazole-4,7-dicarboxylic acid (H BTDC) as the linker
2
this area have been hindered by the photophysical nature of d-
6
electron (major barrier, the nonradiative d-d transition) or
was selected to construct chromophore-derived MOF.
Commonly, benzothiadiazole (BTD) derivative is efficient
2
1
full-filled d-orbital (like Zn(II), absent metal-to-ligand charge
chromophore with fine fluorescence capability, whilst highly
polarized feature of BTD species is beneficial to afford the
transfer state or ligand-to-metal charge transfer state). Hence,
7
chromophore-derived MOF is one more convenient choice.
-12
2
1b
well-ordered crystal structure. On the other hand, planar
BTD unit is a typical electron acceptor, which is beneficial to
trigger the photochemical decarboxylation in suitable
condition. Attractively, if the photochemical decarboxylation
only occurs in the one wing of ligand, the micro-adjustment of
MOF structure can be observed, even that the cavity feature
may be modulated. In this work, we reported the first
exploration for micro-adjustment of MOF strucutre by unique
In the recently several years, a new brilliant scaffold is to
modulate the function of MOF material by light-driven force,
1
3-14
such as photo-induced electron transfer or energy transfer.
In 2016, Zhou group reported an interesting example that can
1
control the generation of singlet Oxygen ( O ) in living cells by
2
1
4b
the tunable ratio of photochromic switch in MOF system.
Obviously, the cases reported in this rising research area are
focused on the application of traditionally photochromic
species.
In contrast, it is beyond unexplored that simple
College of Chemistry and Molecular Engineering, Zhengzhou University, Henan
4
50001, China. E-mail: houhongw@zzu.edu.cn; jieding@zzu.edu.cn.
Electronic Supplementary Information (ESI) available: Crystallographic information
for MOFs Zn-BTDC-M1 Zn-BTDC-M1′ Zn-BTDC-M1′′in CIF format and additional
figures and tables, photophysical properties of Zn-BTDC-M1 See DOI:
0.1039/x0xx00000x
,
,
Scheme 1. Schematic illustration of the photochemical
decarboxylation reaction of Zn-BTDC-M1.
.
1
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photochemical decarboxylation in new benzothiadiazole-
As we know, when photo-induced electron transfer is
occured from carboxylate anion site to benzene ring, rapid loss
derived Zn(II) MOF, Zn-BTDC-M1 (Scheme 1).
In Zn-BTDC-M1, there are three kinds of Zn(II) ions with of CO
different coordination environments, and the neighboring to generate the decarboxylated product. Actually, fast photo-
Zn(II) ions are further linked together through two kinds of induced decarboxylation in H BTDC solution was traced by UV-
2
from carboxy radical site will be subsequently induced
1
6
2
2
-
carboxylate groups of BTDC ligand (Figure S1-S2, Table S1-S3). vis absorption spectroscopy, and the decarboxylated product
1
In detail, one carboxylate group shows bridging tridentate was further comfirmed by H NMR instrument (Figure S9). In
2
1
coordination mode (μ
bidentate bridging coordination fashion (μ
dinuclear {Zn-Zn} unit (Figure S1). The {Zn-Zn} units are Herein, FT-IR spectroscopy analysis is selected to reveal the
2
-η :η ), whilst the other one is a contrast, comparing to Zn-BTDC-M1, such photochemical
1
1
2
-η :η ) to form a process is extremly slow in powdered ligand (Figure S10a).
2
-
connected by BTDC ligands along the special direction to group changes in decarboxylation reactions of Zn-BTDC-M1
construct a 3D framework with 1D rectangular channel along and powdered ligand, respectively (Figure 2a, Figure S10b). In
c axis. On the basis of crystallographic report, Zn-BTDC-M1 (Figure 2a), new peaks at 2335 and 2360 cm
-1
the
1
3
thermogravimetric (TG), C solid state NMR (SSNMR) and corresponding to asymmetrical stretching vibration of free CO2
element analyses, there are non-volatile DMF (DMF = N,N- were remarkably visible under irradiation, which was the
dimethylformamide) molecules in the cavity, which are
diffecultly elimilated even after supercritical CO2 (SC-CO2)
activation (Figure S3). Finally, MOF was outgassed to confirm
removal of DMF molecules, and the phase structure of MOF
was still maintained (Figure S4). Hence, according to the
analyses described above, Zn-BTDC-M1 was defined as
(
[Zn (BTDC) ]⋅1.5DMF. To consider BTD subunit arrangement
2 2
2
2-23
in crystal and reported litertures,
showed non-emissive J-dimmer absorption band at 478 nm
Table S4). Furthermore, only one emission was observed in
Zn-BTDC-M1 obviously
(
Zn-BTDC-M1 with lifetime of 0.99 ns (λem = 430 nm, Figure S5).
More interestingly, MOF Zn-BTDC-M1 displayed an
irreversible photochromic phenomenon. When a visibly color
change was observed under UV irradiation in Zn-BTDC-M1 at
room temperature (Figure S6, movies), no color-recovery was
observed kept in dark for several days. This phenomenon was
totally different from that observed in typical photochromic
system based on energy transfer, which was a possible signal
of reaction triggered by photo-induced electron transfer.
Moreover, new absorption band centered at ~715 nm was
distinctly generated under irradiation in Zn-BTDC-M1 (Figure
1
a, Figure S7). This band was probably anion radical signal of
2
1
BTD species generated by a photo-induced electron transfer,
which was supported by quenched emission behavior under
irradiation (Figure S8). Besides, electron paramagnetic
resonance (EPR) study (Figure 1b) displayed that no EPR signal
was observed in the as-synthesized Zn-BTDC-M1. In contrast, a
signal at g = 2.0045 appeared after irradiation, which was also
supporting the existence of anion radical.
Figure 2. (a) FT-IR spectra of Zn-BTDC-M1 recorded before
and after irradiation. (b) C solid state NMR (SSNMR)
1
3
spectra of Zn-BTDC-M1 (black) and irradiated Zn-BTDC-M1
(red). Asterisks denote DMF molecules in the cavity; inset:
Figure 12 . (a) Absorption spectra of Zn-BTDC-M1 before
and after UV irradiation. (b) EPR spectra of Zn-BTDC-M1
before and after UV irradiation.
the detail in the range of 180-140 ppm. (c) X-ray
photoelectron spectra (XPS) of Zn-BTDC-M1 (blue) and
irradiated Zn-BTDC-M1 (red) showing Zn2p and C 1s peaks.
2
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direct evidence of photo-induced decarboxylation. The initial
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-1
s
υ (C=O) double peaks at 1673/1663 cm were conversed to a
-1
single peak at 1666 cm in the irradiation process, while the
-1
υ(C-O) band at 1216 cm belong to Zn-BTDC-M1 was gradually
weakened (Figure 2a). Especially, a relatively broadened single
-1
peak at 1094 cm was instead of υ(C-O) bands of 1104 and
-
1
1
089 cm in the photochemical process of Zn-BTDC-M1
-1
(
Figure 2a). In fingerprint region (< 1000 cm , Figure 2a), the
-1
signals of typical p-disubstituted benzene rings at 835/816 cm
(C-H wagging) in as-synthesized Zn-BTDC-M1 were gradually
weakened during the photochemical process, especially the
-
-
peak of 835 cm . In contrast, there was a new band at 823 cm
1
1
generated under UV light irradiation in Zn-BTDC-M1
.
Figure 3. (a) The possible pathway A for the dissociation of
carbon dioxide (distance: Å). (b) The possible pathway B
for the dissociation of carbon dioxide (distance: Å). (c)
Proposed scheme of decarboxylation by photo-induced
electron transfer (PET) pathway. (d) Schematic illustration
of the decarboxylation reaction.
Oppositely, such decarboxylation evidences described above
was obscure and difficult to identify in powdered ligand under
irradiation (Figure S10b), which was consistent to the UV-vis
absorption analysis.
Moreover, when photochemical decarboxylation reaction
1
3
was occurred in Zn-BTDC-M1
,
C SSNMR spectra should be
visibly shorter than that in non-chelated wings (C9-C10:
1.503(5)/C1-C2: 1.503(5) Å). It supported that such C-C bond
breaking in C1-C2/C9-C10 was easier than that in C5-C8/C13-
C16. On the other hand, the dihedral angles between BTD rings
and carboxylate planes were changed in the irradiation
process (Table S5), which could relatively influence the
electron cloud distribution of ligand. Herein, we speculate that
sensitively traced the weakened or completely disappeared
1
3
peak of carboxyl group. As we expect, the C SSNMR analysis
Figure 2b) suggested that comparing to the initial intensity of
the typical carboxyl group peak at 174.3 ppm in Zn-BTDC-M1
its intensity was less than one third in irradiated Zn-BTDC-M1
whilst no such changes were observed in the remaining peaks
(
,
,
2
-
of BTDC linker. Except for these, XPS spectra of Zn-BTDC-M1
-
-
•
it may delay the anionic radical ( OOC−BTD−COO ) decay to
before and after irradiation indicated that as shown in Figure
enlarge the probability of subsequent decarboxylation.
Moreover, molecular modeling analysis shows that the
decarboxylation energy barrier on non-chelated wings of
2
c, the two peaks of Zn 2p1/2 and 2p3/2 in as-synthesized Zn-
BTDC-M1 was appearing at 1045.5 and 1022.4 eV, respectively,
while for the irradiated sample, such binding energies shifted
towards a higher energy of 1045.6 and 1022.8 eV, respectively.
In addition, the separation of the binding energy between
2
-
BTDC is only 5.3 kcal/mol, indicating a smoothly pathway
2
Figure 3a). In contrast, in chelated wings of BTDC , the
-
(
decarboxylation can be excluded, because of the intermediate
state hardly located with an energy barrier distinctly higher
than 40 kcal/mol (Figure 3b). Hence, we speculated that the first
step of photochemical decarboxylation was photo-induced electron
transfer. When Zn-BTDC-M1 was irradiated by UV light, electrons
would tranfer from groud state (GS) to excited state (ES, Figure 3c).
2
p1/2 and 2p3/2 decreases from 23.1 to 22.8 eV. These results
imply the relatively changed coordination environment of
2
4
metallic zinc during the photochemical reaction. At the same
time, in C1s XPS spectrum of as-synthesized Zn-BTDC-M1, the
typical C=C/C-C peak was at 284.8 eV, while their oxidative
2
5
form peaks located at 286.0 eV (C-O) and 288.5 eV (C=O). For
irradiated Zn-BTDC-M1, the C=C/C-C peak was shifted to 285.2
eV, the intensity of which was visibly enhanced. Interestingly,
the intensities of shifted oxidative form peaks were oppositely
weakened in irradiated Zn-BTDC-M1 (Figure 2c). Obeviously,
this evidence was further reveal the photochemical
decarboxylation process in material designed. Accoring to
these results, photochemical decarboxylation process should
-
Subsequently, the photo-induced electron transfer from COO
groups to BTD moieties was tending to occur at non-chelated wings
2
-
of BTDC because of small energy barrier. In the last step, free CO
2
2
-
were generated, and non-chelated wings of BTDC were
decarboxylated (Figure 3c-3d).
Furthermore, physical N
chemical NH gas adsorption (Figure S13) studies were
accomplished to explore the cavity feature before and after
structural micro-adjustment by photochemical
decarboxylation in Zn-BTDC-M1 case. Comparing to small
2
adsorption (Figure S12) and
3
2
-
be occurred at one wing of BTDC . Because of the suitable
restricted media we designed (Zn-BTDC-M1), it is much easier
than pure ligand in solid state.
2
1
surface area of Zn-BTDC-M1 (Table S6), it was distinctly
Significantly, PXRD data before and after irradiation (Figure
S11) showed that main framework of Zn-BTDC-M1 was
enlarged in irradiated one, especially the Langmuir surface
area. On the other hand, NH
3
gas adsorption capability of
gas
maintained,
indicating
a
crystalline-to-crystalline
material is very sensitive to its acidity. As we expect, NH
3
transformation feature. Based on this, control structure
adsorption experiment (Table S7) demonstrated that the
adsorption capability of irradiated material was weaker than
that of as-synthesized material, which was resulted from the
decreased acidity by photochemical decarboxylation.
experiments of Zn-BTDC-M1 before and after irridiation were
analysed
(Zn-BTDC-M1, Zn-BTDC-M1′ and Zn-BTDC-M1′′,
collected by the same single crystal, as seen in movies). In Zn-
BTDC-M1, C-C bond connected with BTD and carboxyl groups
in chelated wings (C13-C16: 1.487(5)/C5-C8: 1.491(6) Å) is
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1
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Conclusions
In summary, a new benzothiadiazole-derived Zn(II) MOF Zn-
BTDC-M1 showed the unique crystalline-to-crystalline micro-
adjustment of structure by photochemical decarboxylation
process. This first exploration in the BTD-derived MOF will
extremely inspire more and more photochemical routes to
modulate function MOFs materials in foreseeable future.
1
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