Structural tuning of zinc-porphyrin frameworks: Via auxiliary nitrogen-containing ligands towards selective adsorption of cationic dyes

Article abstract of DOI:10.1039/c9cc02405k

Three metal-organic frameworks have been synthesized by using N-containing ligands and meso-tetra(4-carboxyphenyl)porphyrin, which all exhibit distinct selective adsorption capacities toward various organic dyes, illustrating the most important influence of the structural tuning.

Full text of DOI:10.1039/c9cc02405k

View Article Online
View Journal
ChemComm
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: X. Wang, J. Li, Y.
Zhao, J. Pang, B. Li, T. Zhang and H. Zhou, Chem. Commun., 2019, DOI: 10.1039/C9CC02405K.
Volume 52 Number
1
4
January 2016 Pages 1–216
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
ChemComm
Chemical Communications
www.rsc.org/chemcomm
Accepted Manuscripts are published online shortly after
acceptance, before technical editing, formatting and proof reading.
Using this free service, authors can make their results available
to the community, in citable form, before we publish the edited
article. We will replace this Accepted Manuscript with the edited
and formatted Advance Article as soon as it is available.
You can find more information about Accepted Manuscripts in the
author guidelines.
Please note that technical editing may introduce minor changes
to the text and/or graphics, which may alter content. The journal’s
standard Terms & Conditions and the ethical guidelines, outlined
in our author and reviewer resource centre, still apply. In no
event shall the Royal Society of Chemistry be held responsible
for any errors or omissions in this Accepted Manuscript or any
consequences arising from the use of any information it contains.
ISSN 1359-7345
COMMUNICATION
Marilyn M. Olmstead, Alan L. Balch, Josep M. Poblet, Luis Echegoyenet al.
Reactivity differences of Sc
first methanofullerene derivatives of Sc
3
N@C2n (2n
=
68 and 80). Synthesis of the
3
N@D5h-C80
rsc.li/chemcomm

Page 1 of 5
Please d oC hn eo mt Ca do mj u ms t margins
View Article Online
DOI: 10.1039/C9CC02405K
Journal Name
COMMUNICATION
Structural Regulation of Zinc-Porphyrin Frameworks via the
Auxiliary Nitrogen-containing Ligands towards the Selective
Adsorption of Cationic Dyes
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
b
a,
a
Xiao-ning Wang, Jiang-li Li, Yu-meng Zhao, Jian-dong Pang, Bao Li *, Tian-Le Zhang and Hong-
DOI: 10.1039/x0xx00000x
Cai Zhoub,*
www.rsc.org/
Three Metal–Organic Frameworks have been synthesized by using most of the porphyrinic MOFs exhibits the low-dimensional
the N-containing ligands and meso-tetra(4- topologies and limited application due to their routine
carboxyphenyl)porphyrin , which all exhibit the distinct selective coordination habits. For example, the utilization of meso-
adsorption capacity toward various organic dyes, illustrating the tetra(4-carboxyphenyl)porphyrin (H TCPP) reacted with zinc ion
6
most important influence of the structural characteristics.
tends to facilitate the two dimensional framework. To break
through the bondage of the coordination pattern of these
porphyrinic linkers, the introduction of versatile nitrogen-
containing ligands that possess variable coordination modes
would be of an effective way to further explore the structural
diversities and functionalities of porphyrinic MOFs. Herein, in
order to establish a successful demonstration about the
synergistic effect between the porphyrine and auxiliary linkers,
In the past few decades, the emergence of Metal-Organic
Frameworks (MOFs) crystalline materials with tunable pore size
and modifiable pore surfaces has motivated the intensive
1
,2
interest owing to their widely potential applications. In
contrast to the extensive investigations focused on gas-
3
4,5
6
adsorption properties , catalysis as well as chemical sensing ,
studies over the application of MOFs in biomimicry and
biological fields still remains relatively underdeveloped. The
presented results have shown that the rational regulation of
porous structure, chemical environment and surface
functionality of pore channels of MOFs would facilitate their
three microporous porphyrinic MOFs, [(NH
2
Me
(H O)
(3), (bentz
2
)][Zn
3
(TCPP)
(bentz)] (1), [(NH
2
Me
2
)
2
][Zn6.5(TCPP)1.5(tz)
O) (ade) (μ -O)
6
2
6
] (2) and
[
(NH Me ][Zn (TCPP)
2
2
)
6
9
3
(H
2
2
2
2
2
]
=
benzotriazole, Htz = 1H-1,2,3-triazole, ade = adenine ), had been
synthesized (Scheme S1, ESI†). Structural characterizations
reveal the specific synergistic effects caused by the
combinations of TCPP and versatile zinc clusters. Especially for
7
applications in biological field.
Due to the intrinsic biological relevance, the incorporation of
biomimic functionalities into MOF frameworks has been
demonstrated as an efficient way to construct the nucleobase-
incorporated MOFs.7b However, except for a limited number of
flexible metal-peptide frameworks that mimic the
conformational adaptability of proteins, nucleobase-
3
, open Watson-Crick planar constructed by adenine and TCPP
had been embellished periodically in the interior surface of the
anionic framework, which might be responsible for the
excellent adsorption of dye molecules.
Due to the distinct coordination habits of the selected
auxiliary ligands, three new MOFs with the different zinc
clusters and topological structures had been characterized. 1
crystallizes in the orthorhombic space group Pnnm with an
8
incorporated MOFs has been rarely explored. Recently, MOFs
consisted of the substituted porphines and metalloporphyrins
has received great attention due to their excellent structural-
activity relationship.9 Viewed from the presented structures,
-11
2+
asymmetric unit consisting of three Zn ions, one TCPP and one
benzotriazole (Figure S1a, ESI†). Zn1 and Zn3 atoms are five-
coordinated with four oxygen atoms from different TCPP
ligands and one nitrogen atom from benzotriazole. The typical
a. Key laboratory of Material Chemistry for Energy Conversion and Storage, School of
Chemistry and Chemical Engineering, Huazhong University of Science and
Technology, Wuhan, Hubei, 430074，PR China. E-mail: libao@hust.edu.cn.
2 4
Zn (COO) paddle-wheel clusters had been fabricated via the
symmetric growth of Zn1 or Zn3 atom, whose apical sites are
occupied by benzotriazole molecules. Zn2 and Zn4 atoms are
exclusively bind by four pyrrole nitrogen atoms. In this way,
each TCPP connects four paddle-wheel clusters and chelates
one zinc ion to form the 2D porphyrin layer. The benzotriazole
ligands act as pillars, and extend the adjacent 2D layers to form
b. Department of Chemistry, Texas A&M Energy Institute, Texas A&M
University,College Station, Texas 77843-3255, United States. E-mail:
zhou@chem.tamu.edu
†
Footnotes relating to the title and/or authors should appear here.
Electronic Supplementary Information (ESI) available: Additional experimental
sections, characterization and physical measurements (PDF). X-ray crystallographic
data for 1-3 (CIF). CCDC 1848723-1848725. For ESI and crystallographic data in CIF
or other electronic format see DOI: 10.1039/x0xx00000x
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

Please d oC hn eo mt Ca do mj u ms t margins
Page 2 of 5
COMMUNICATION
Journal Name
a 3D porous framework that contains 1D quadrangle different tz, two carboxylate oxygen atom from tVwiewoAdrtiicflfeeOrnelinnet
microporous channels along the c axis (Fig. 1a). Zn-O and Zn-N TCPP ligands and one coordinated waDtOeIr: 1m0.1o0l3e9c/uCl9eC.CZ0n24505iKs
distances fall in the range from 1.846(7) to 2.160(6) Å, while exclusively coordinated by six nitrogen atoms from six tz, which
Zn···Zn distance is 2.9478(18) Å, in accordance with the typical locates in the center and connects other four zinc ions via tz to
1
2
4+
values of Zn
2 5 6
cluster. The total solvent accessible volume in 1 form the penta-nuclear r[Zn (tz) ] clusters (Figure S2b, ESI†).
3
3
is ascertained to be 59% (11298.5 Å /19070.5 Å ), calculated The perpendicular of Zn5 cluster is further decorated by six
by the PLATON routine.
TCPP ligands to generate a 3D framework, which possesses 1D
rhombus-shaped channel along the c axis (Fig. 1b). A PLATON
calculation indicates
approximately 65% (6286.1 Å /9647.0 Å ) in the final
a
solvent-accessible volume of
3
3
framework.
Fig. 2 (a) Partial view of the 3D framework of 3; (b) A fragment showing the hexa-nuclear
cluster, the open Watson-Crick faces and the uncoordinated carboxyl-O sites; (c) The
topological network of 3. (blue square represents TCPPP; purple and green polyhedrons
represent Zn clusters)
Fig. 1 (a) Partial view of the 3D framework of 1 along the c axis; (b) Partial view of the 3D
framework of 2 along the c axis; (c) The topological network of 1; (d) The topological
network of 2. ( Purple square and green polyhedron represent TCPP and Zn cluster)
Differently, 3 crystallizes in the triclinic P-1 space group (see
2
+
Table S1, ESI†). The asymmetric unit of 3 contains nine Zn ion,
three TCPP ligands, two adenine ligands, two µ -O and two
Comparably, 2 crystallizes in triclinic P-1 space group, which coordinated water molecules (Figure S4, ESI†). The vacancy of
2
2
+
comprises six and half Zn ions, one and half TCPP ligands, six TCPP had been occupied by zinc ions ( Zn7, Zn8 and Zn9 ).Three
tz ligands and six coordinated water molecules in one connection types of TCPP had been observed and illustrate in
asymmetric unit (Figure S2a, ESI†). The vacancy of TCPP ligands Figure S5, ESI†, which separately connects four, five and six zinc
have been occupied by zinc ions (Zn6 and Zn7). There are two ions. Due to the synergistic effect between ade and TCPP,
types of the carboxylate groups on TCPP(Figure S3, ESI†): the diverse connection modes and novel configurations of zinc
carboxylate substitutes on one type of TCPP adapt the chelating clusters had been stabilized. The coordination sites of Zn1-Zn4
2
+
mode to connect four Zn ions; the other ones are the mono- had been occupied by one adenine-N, two carboxylate O atoms
2
+
dentate carboxylates to connect four Zn ions. Furthermore, from two TCPP ligands and one μ
Zn1 and Zn4 atoms are five-coordinated with three nitrogen Zn4 are bind together to form the di-nuclear cluster via μ1,3
atoms from different tz, two oxygen atoms from one bridging ade and µ -O atom. Zn5 or Zn6 atoms adapts the
carboxylate and one coordinated water molecule. Zn2 and Zn3 tetragonal pyramid geometry to form the typical Zn (COO)
atoms are six-coordinated with three nitrogen atoms from paddlewheel, whose axial positions are occupied by adenine-N
2
-O atom. Zn1 and Zn2/Zn3 and
-
2
2
4
2
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 5
Please d oC hn eo mt Ca do mj u ms t margins
Journal Name
atoms. Through the connection of ade, the paddlewheel cluster
COMMUNICATION
The proper porous traits of these MOFs encoVuierwagAertidcleuOsnlitnoe
had been extended to form the hexa-nuclear cluster (Fig. 2b), further explore the adsorption ability foDrOdI:y1e0s.1m03o9/leCc9uClCe0s2w40i5thK
which is further decorated by twelve TCPP ligands to form the different size and charge. In order to acquire a systematic
final framework. 1D rhombus-shaped channel had been left in insight into the dye-adsorption properties for 1-3, two
the final framework (Fig. 2a). The open Watson-Crick faces and comparable sets of tests had been carried out: In the first group,
the uncoordinated carboxyl-O sites had been decorated on the three dyes with the similar size and different charges
+
0
−
surface of the channel, which endows 3 with the potential (methylene blue: MB ; neutral red: NR ; methyl orange: MO )
adsorption ability towards the specific molecules. A PLATON had been selected as the target guest molecules. The main
+
calculation indicates
a
solvent-accessible volume of absorption intensity of MB at 664 nm significantly drops with
3
3
approximately 75% (15858.2 Å /21050.7 Å ) in the final the passage of time and the blue solution also faded to become
+
framework.
colorless, indicating that MB has been adsorbed by 1-3 via ion-
(Fig. 4a and Figure S16a,18a, ESI†).
However, the unchanged concentration of NR and MO
+
exchange with Me
NH
2 2
0
-
-
indicate that the neutral NR and anionic MO dyes cannot be
adsorbed by 1-3 although with the accessible sizes (Figure S13,
1
4, ESI†). These experimental results illustrate that the dye
adsorption behaviors for 1-3 could only take place towards
cationic ones, in consistent with the principle of ionic effect.
Fig. 3 N
2
physisorption isotherms for 1-3 at 77 K (a); CO
2
adsorption isotherms for 1-3 at
2
73 K (b); C H
2 2
adsorption isotherms for 1-3 at 273 K (c).
The purity of these synthesized samples had been checked via
PXRD experiments (Figure S7-9, ESI†), which gives the matched Fig. 4 UV-vis spectra of DMF solutions of methylene blue (MB ) (a), basic violet 14 (BV14 )
+
+
+
(
b), and rhodamine 6G (Rh6G ) (c) in the presence of complex 3 at different times. The
inset images display the change in colors before and after the dye adsorption by complex
. (d) Adsorption kinetics and the corresponding plots of pseudo-second order fitting
spectra with the simulated ones. The thermal stability of these
samples had been also measured (Figure S10-12, ESI†). Due to
the introduction of auxiliary ligands, the high thermal stability
had been presented for 1-3. Thanks to the large channel and
low framework density, the porous traits of these zinc-
3
plots of 1-3 towards MB.
To further verify the selectivity of dyes with different charges,
the samples of 1-3 had been immersed in the mixtures of MB
and NR , MB & MO with equal concentration, respectively (Fig.
, Figure S17,19, ESI†). It is obviously that the adsorption
porphyrin frameworks had been characterized via
N
2
+
adsorption at 77 K (Fig. 3a). The activated samples of 1-3 could
0
+
-
3
-1
adsorb 138, 200, 286 cm g N
2
, respectively, along with the
5
calculated BET surface area/Langmuir surface area of
+
intensity of the peak for MB (664 nm) decreases along with the
2
−1
2
−1
3
6
N
73.5/551.4 m
g
for 1, 456.1/678.2 m
g
for 2 and
0
-
unchanged peaks for NR (453 nm) and MO (421 nm).
Meanwhile, the color of the mixed solutions slowly turned from
green to orange after 5 h, respectively. This experimental
phenomenon obviously illustrates the selective adsorption of
different dye molecules, in consistent with the structural
characteristics of 1-3 such as anionic framework and large
porosity. Apart from this, the adsorption mechanism might be
ascribed to the ion-exchange process, which endows 1-3 with
the potential application as charge-dependent adsorbent for
the selective separation of organic dyes.
2
−1
22.8/918.5 m g for 3. Furthermore, the type-I isotherms of
2
adsorption illustrate the micro-porous characteristics for the
activated 1-3. Furthermore, these frameworks also exhibit the
proper adsorption abilities towards the small molecules as CO
and C , illustrating the existence of strong adsorption sites in
2
2 2
H
the channels of frameworks. The increasing parameters of
porous surfaces and amounts of the guest molecules are in
consistent with the structural characteristics of three MOFs,
further manifesting the important role of the auxiliary nitrogen-
containing ligands to regulate the porous structures of Zinc-
Porphyrin Frameworks.
+
+
The second set of dyes includes MB , basic violet 14 (BV14 )
and rhodamine 6G (R6G ), which have the same charge but
+
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

Please d oC hn eo mt Ca do mj u ms t margins
Page 4 of 5
COMMUNICATION
Journal Name
different sizes (Table S5, ESI†). The adsorption experiments Center, Huazhong University of Science and Technology, for
View Article Online
DOI: 10.1039/C9CC02405K
manifested that all of these MOFs exhibit the quick adsorption analysis and spectral measurements.
ability (Fig. 4, Figure S16, 18, ESI†), but with the different
+
adsorption degree for three cationic dyes. For MB , 91.1%, 91.3%
and 92% of dye concentration can be absorbed by the solid
Conflicts of interest
samples of 1-3 after 5 h, respectively, illustrating the excellent
adsorption abilities of these MOFs. For BV14 and R6G under
There are no conflicts to declare.
+
+
the same testing conditions, the adsorption ratio of 1-3 were
calculated to be 64%, 70.8%, and 75.8% as well as 35.8%, 50%, Notes and references
and 59.5%, respectively. The kinetic rate constants for the
adsorption of three dyes in 1-3 had been calculated, in
consistent with the marcoscopic phenomenons (Table S6, ESI†).
1
2
3
(a) S. Kitagawa and K. Uemura, Chem. Soc. Rev., 2005, 34, 109; (b) G.
Férey and C. Serre, Chem. Soc. Rev., 2009, 38, 1380; (c) H. C. Zhou, J.
R. Long and O. M. Yaghi, Chem. Rev., 2012, 112, 673.
(a) K. Sumida, D. L. Rogow, J. A. Mason, T. M. McDonald, E. D. Bloch,
Z. R. Herm, T.-H. Bae and J. R. Long, Chem. Rev., 2012, 112, 724; (b) J.-
R. Li, J. Sculley and H.-C. Zhou, Chem. Rev., 2012, 112, 869.
(a) L. Zhang, K. Jiang, L. Li, Y. Xia, T. Hu, Y. Yang, Y. Cui, B. Li, B. Chen
and G. Qian, Chem. Commun., 2018, 54, 4846; (b) K. Adil, Y.
Belmabkhout, R. S. Pillai, A. Cadiau, P. M. Bhatt, A. H. Assen, G. Maurin
and M. Eddaoudi, Chem. Soc. Rev., 2017, 46, 3402.
The difference should be ascribed to the sized effect of dyes
+
(
Table S5, ESI†). The smallest MB molecules are able to easily
enter into the pore of these MOFs, which gives the largest
kinetic rate constant compared to other two dyes. In addition,
the largest pore dimension in 3 must be responsible for the
+
better adsorption efficiency towards the larger dyes as BV14
and R6G compared to 1 and 2.
4
(a) Y. Yang, C. Gao, H. Tian, J. Ai, X. Min and Z. Sun, Chem. Commun.,
+
2
018, 54, 1758; (b) J. Liu, L. Chen, H. Cui, J. Zhang, L. Zhang and C. Y.
Su, Chem. Soc. Rev., 2014, 43, 6011; (c) J. Baek, B. Rungtaweevoranit,
X. Pei, M. Park, S. C. Fakra, Y. Liu, R. Matheu, S. A. Alshmimri, S.
Alshehri, C. A. Trickett, G. A. Somorjai and O. M. Yaghi, J. Am. Chem.
Soc., 2018, 140, 18208.
5
6
(a) M. J. Katz, S. Moon, J. E. Mondloch, M. H. Beyzavi, C. J. Stephenson,
J. T. Hupp and O. K. Farha, Chem. Sci., 2015, 6, 2286. (b) M. Ding and
H. Jiang, ACS. Catal., 2018, 8, 3194. (c) Q. Yang, Q. Xu and H. Jiang,
Chem. Soc. Rev., 2017, 46, 4774. (d) Y. Huang, J. Liang, X. Wang and R.
Cao, Chem. Soc. Rev., 2017, 46, 126.
(a) Y. Cui, Y. Yue, G. Qian and B. Chen, Chem. Rev., 2011, 112, 1126;
(
b) Z. Hu, B. J. Deibert and J. Li, Chem. Soc. Rev., 2014, 43, 5815; (c) W.
+
0
+
-
Fig. 5 UV-Vis absorption spectra of equimolar MB & NR (a) and MB & MO (b) in the
presence of the complex 3 at different times. The inset images display the change in
colors before and after the dye adsorption by complex 3.
P. Lustig, S. Mukherjee, N. D. Rudd, A. V. Desai, J. Li and S. K. Ghosh,
Chem. Soc. Rev., 2017, 46, 3242.
(a) M. Zhang, Z. Gu, M. Bosch, Z. Perry and H. Zhou, Coord. Chem. Rev.,
7
8
9
2
015, 293, 327; (b) I. Imaz, M. Rubio-Martínez, J. An, I. Solé-Font, N.
In summary, by introducing the versatile auxiliary ligands,
three novel zinc-porphyrin MOFs had been constructed. All of
these MOFs exhibit the distinct 3D extended structures
fabricated including the different zinc clusters and topological
structures, which must be ascribed to the synergistic effect
between the porphyrinic linker and versatile N-donor ligands.
Especially for 3, the open Watson-Crick planar in the interior
surface has been presented. Benefiting from the structural
traits as the high porosity and anionic framework, all of these
MOFs can selectively adsorb cationic organic dyes in solution.
L. Rosi and D. Maspoch, Chem. Commun., 2011, 47, 7287.
(a) G. Beobide, O. Castillo, J. Cepeda, A. Luque, S. Pérez-Yáñez, P.
Román, J. Thomas-Gipson, Coord. Chem. Rev., 2013, 257, 2716; (b) P.
Amo-Ochoa and F. Zamora, Coord. Chem. Rev., 2014, 276, 34.
(a) M. H. Beyzavi, N. A. Vermeulen, A. J. Howarth, S. Tussupbayev, A.
B. League, N. M. Schweitzer, J. R. Gallagher, A. E. Platero-Prats, N.
Hafezi, A. A. Sarjeant, J. T. Miller, K. W. Chapman, J. F. Stoddart, C. J.
Cramer, J. T. Hupp and O. K. Farha, J. Am. Chem. Soc., 2015, 137,
1
3624. (b) J. A. Johnson, B. M. Petersen, A. Kormos, E. Echeverría, Y.
Chen and J. Zhang, J. Am. Chem. Soc., 2016, 138, 10293. (c) G. Lin, H.
Ding, D. Yuan, B. Wang and C. Wang, J. Am. Chem. Soc., 2016, 138,
3302; (d) S. Huh, S. -J. Kim and Y. Kim, CrystEngComm, 2016, 18, 345.
The pore dimension and charged framework must be 10 (a) J. Pang, S. Yuan, J. Qin, M. Wu, C. T. Lollar, J. Li, N. Huang, B. Li, P.
Zhang and H. Zhou, J. Am. Chem. Soc., 2018, 140, 12328; (b) P. Deria,
D. A. Gómez-Gualdrón, I. Hod, R. Q. Snurr, J. T. Hupp and O. K. Farha,
J. Am. Chem. Soc., 2016, 138, 14449; (c) W. Morris, B. Volosskiy, S.
Demir, F. Gándara, P. L. McGrier, H. Furukawa, D. Cascio, J. F. Stoddart
responsible for the origination of the different adsorption
behaviors. The presented results have expanded the
coordination diversities of porphyrin-based MOFs, and
illustrating the important role of the synthesis strategy for
fabricating the anticipated MOF materials.
and O. M. Yaghi, Inorg. Chem., 2012, 51, 6443.
11 (a) N. Huang, K. Wang, H. Drake, P. Cai, J. Pang, J. Li, S. Che, L. Huang,
Q. Wang and H. Zhou, J. Am. Chem. Soc., 2018, 140, 6383; (b) Z. Zhang,
L. Zhang, L. Wojtas, P. Nugent, M. Eddaoudi and M. J. Zaworotko, J.
Am. Chem. Soc., 2011, 134, 924.
2 (a) G. Dutta, A. K. Jana and S. Natarajan, Chem. - Eur. J., 2017, 23,
8932; (b) W. Fan, H. Lin, X. Yuan, F. Dai, Z. Xiao, L. Zhang, L. Luo and R.
Wang, Inorg. Chem., 2016, 55, 6420.
We gratefully acknowledge the National Natural Science
Foundation of China (No. 21471062), the Center for Gas
Separations Relevant to Clean Energy Technologies, an Energy
Frontier Research Center (EFRC) funded by the U.S. Department
of Energy (DOE), Office of Science, and Office of Basic Energy
Sciences (DESC0001015), Office of Fossil Energy, the National
Energy Technology Laboratory (DE-FE0026472), and the Robert
A. Welch Foundation through a Welch Endowed Chair to HJZ (A-
1
0
030) for financial support, and the Analytical and Testing
4
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 5
ChemComm
View Article Online
DOI: 10.1039/C9CC02405K
Structural Regulation of Zinc-Porphyrin Frameworks via the
Auxiliary Nitrogen-containing Ligands towards the Selective
Adsorption of Cationic Dyes
Three novel zinc-porphyrin MOFs have been synthesized by using versatile N-containing ligands.
The open Watson-Crick planar in the interior surface in one Zn-MOF has been presented, which
could endow the related MOF with the excellent selective adsorption of dye molecules.