Syntheses, structures and luminescence properties of five coordination polymers based on designed 2,7-bis(4-benzoic acid)-: N -(4-benzoic acid) carbazole

Article abstract of DOI:10.1039/c7ce00361g

Herein we report five porous luminescent coordination polymers (CPs), namely, [Zn₃(L₂₇)₂(DMA)₆(H₂O)₄]_n (TCZ-001), [Zn₃(L₂₇)₂(DMA)₆(CH₃CH₂OH)₂]_n (TCZ-002), [Zn₃(L₂₇)₂(DMA)₆(CH₃OH)]_n (TCZ-003), [Cd₃(L₂₇)₂(DMA)₆(H₂O)₂]_n (TCZ-004), and [Cd₉(L₂₇)₆DMA₁₃(4,4′-BPY)₂(OH)₂(H₂O)_13.5]_n (TCZ-005) [H₃L₂₇ = 2,7-bis(4-benzoic acid)-N-(4-benzoic acid) carbazole, DMA = N,N-dimethylacetamide, 4,4′-BPY = 4,4′-bipyridine, TCZ = "T"-shape carbazole-based polymers, L₂₇ = fully deprotonated H₃L₂₇^3- ligand]. All of the five CPs were assembled from a novel luminescent carbazole-based ligand. X-ray crystallography showed that TCZ-001 is a 3-connected one-dimensional (1D) chain structure with a {4²·6} topology. TCZ-002 possesses a 3,6-connected three-dimensional (3D) framework with a point symbol of {4²·6}₂{4⁴·6²·8⁷·10²}. TCZ-003 displays a 3,6-connected two-dimensional 2D network with a Schl?fli symbol of {4¹¹·6⁴}·{4³}₂, which is a new topology. TCZ-004 features a 3,6-connected 2D net with a {4³}₂·{4⁶·6⁶·8³} topology. In TCZ-005, the structure can be classified into two groups: one of the two groups is a 3-connected 1D chain structure with a {4²·6} topology, similar to TCZ-001; the other one possesses a 3,3,3,4-connected network with a Schl?fli symbol of {4²·6³·8}{4²·6}₃. The structure of TCZ-005 could be described as an SP 1-periodic net (4,4)(0,2) in the 1D-2D.ttd database. TCZ-001, TCZ-003 and TCZ-004 show a remarkable response to the Ni²⁺ concentration in DMA, H₂O or EtOH. Some of Zn²⁺ ions were replaced by Ni²⁺ ions and the rate of the transmetalation depended on the concentration of Ni²⁺ ions. Also, changing part of the metal node would transform the colour of emitted light. Additionally, the colour of the luminescence displays a linear correlation with the Ni²⁺ concentration range from 0.005 to 0.35 M (mol L^-1). Besides selective sensing of Ni²⁺, TCZ-004 can also be utilized to detect Eu³⁺ in DMA solution. Thus, several potential sensory probe materials for Ni²⁺ and Eu³⁺ detection in DMA solution have been obtained.

Full text of DOI:10.1039/c7ce00361g

View Article Online
View Journal
CrystEngComm
Accepted Manuscript
This article can be cited before page numbers have been issued, to do this please use: D. Chen, L. Lin, T.
Sheng, Y. Wen, S. Hu, R. Fu, C. Zhuo, H. Li and X. Wu, CrystEngComm, 2017, DOI: 10.1039/C7CE00361G.
Volume 18 Number 1 7 January 2016 Pages 1–184
This is an Accepted Manuscript, which has been through the
Royal Society of Chemistry peer review process and has been
accepted for publication.
CrystEngComm
Accepted Manuscripts are published online shortly after
www.rsc.org/crystengcomm
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.
HIGHLIGHT
Tiddo J. Mooibroek, Antonio Frontera et al.
Towards design strategies for anion–π interactions in crystal engineering
rsc.li/crystengcomm

Page 1 of 12
PleaseC dr oy sn t oE tn ag dCj uo smt mm argins
View Article Online
DOI: 10.1039/C7CE00361G
CrystEngComm
ARTICLE
Syntheses, structures and luminescence properties of five
coordination polymers based on designed 2,7-bis(4-benzoic acid)-
N-(4-benzoic acid) carbazole
Received 00th January 20xx,
Accepted 00th January 20xx
ab
ab
a
a
a
a
DOI: 10.1039/x0xx00000x
Dong-Hui Chen , Ling Lin , Tian-Lu Sheng , Yue-Hong Wen , Sheng-Min Hu , Rui-Biao Fu , Chao
ab ab a
Zhuo , Hao-Ran Li and Xin-Tao Wu*
www.rsc.org/
Herein we report five porous luminescent coordination polymers (CPs), [Zn
3
(L27
)
2
(DMA)
6
(H
2
O)
4
]
n
(TCZ-001),
(TCZ-004),
[
[
Zn
Cd
3
(L27
)
2
(DMA)
6
(CH
3
CH
2
OH)
2
]
n
(TCZ-002), [Zn
3
(L27
)
2
(DMA)
6
(CH
3
OH)]
n
(TCZ-003), [Cd
3
(L27
2
) (DMA)
6
(H
2
O)
2 n
]
9
(L27
)
6
DMA13(4,4’-BPY)
2
(OH)
2
(H (TCZ-005) [H
2
O)13.5
]
n
3
L27 = 2,7-bis(4-benzoic acid)-N-(4-benzoic acid) carbazole, DMA =
N,N-dimethylacetamide, 4,4’-BPY = 4,4'-bipyridine, TCZ = “T”-shape carbazole-based polymers, L27 = fully deprotonated
3-
3
H L
27 ligand]. All of the five CPs were assembled from a novel luminescent carbazole-based ligand. X-ray crystallography
2
showed that TCZ-001 is a 3-connected one-dimensional (1D) chain structure with a {4 .6} topology. TCZ-002 possesses a
2
4
2
7
2
3
,6-connected three-dimensional (3D) framework with a point symbol of {4 .6}
2
{4 .6 .8 .10 }. TCZ-003 displays a 3,6-
11
4
3
connected two-dimensional 2D network with a Schläfli symbol of {4 .6 }.{4 }
2
, which is a new topology. TCZ-004 features a
3
6
6
3
3
,6-connected 2D net with a {4 }
2
.{4 .6 .8 } topology. In TCZ-005, the structure can be classified into two groups: One of
2
the two groups is a 3-connected 1D chain structure with a {4 .6} topology, similar to TCZ-001; The other one possesses a
2
3
2
3
,3,3,4-connected network with a Schläfli symbol of {4 .6 .8}{4 .6}
3
. The structure of TCZ-005 could be described as a SP 1-
2+
periodic net (4,4)(0,2) in the 1D_2D.ttd database. TCZ-001, TCZ-003 and TCZ-004 show a remarkable response to Ni
2+
2+
concentration in DMA, H
2
O or EtOH. Part of Zn ions were replaced by Ni ions and the rate of the transmetalation
2+
depended on the concentration of Ni ions. And changing part of the metal node would transform the colour of emmitting
2+
light. Additionally, the colour of the luminescent display a linear correlation with the Ni concentration range from 0.005
2+
3+
to 0.35M (mol/L). Besides selective sensing of Ni , TCZ-004 can also be utilized to detect Eu in DMA solution. Thus,
2+
3+
several potential sensory probe materials for Ni and Eu detection in DMA solution have been obtained.
2+
remains rare. Moreover, sensing Ni ions concentration
according to colour of the emitting light is much more
infrequent. Undoubtedly, luminescence-based detection of
Introduction
Coordination polymers (CPs) or metal-organic complexes
2+
Ni ions concentration is much simpler than the traditional
method by the dimethylgyoxmine spectrophotometry, which
(MOCs), assembled from organic linkers and metal nodes, have
been explored for potential application in fluorescence
3
0
1-4
5
6,7
8
need professional technician and instrument. And another
method that figuring out the ions concentration is basing on
the intensity of the emission spectra of probe material in
various concentrations of ions. But this method requires
sensors,
separation, gas sorption and catalysis. The
flexibility of organic linkers and metal nodes provides the
opportunity for engineering the optical properties
2
,4
and
9
structure of the CPs. Recently a recent surging in luminescent
CPs utilized to detect metal ions, volatile organic compounds
3
1,32
confirming the standards before measuring.
Therefore, a
10-18
more convenient and rapid method need to be created and
and anions,
especially in detecting heavy and lanthanide
2+
3+
2+
2+
2+
+
2+
2+
2+
6+
used in detecting Ni concentration. Meanwhile, sensing Eu
metal ions, such as Co , Cu , Mn , Ag , Zn , Cd , Hg , Cr ,
3+
3+
3+ 19-29
2+
concentration in DMA solution rapidly based on the colour of
emitting light is also unusual. Herein, a family of new CPs was
designed specifically to address this problem and the solution
to this can be explored with a focus on the luminescent
property of the ligand.
Fe , Eu and Tb .
But selectively detecting Ni ion
a.
State Key Laboratory of Structure Chemistry, Fujian Institute of Research on the
Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, Fujian, PR
China.
Carbazole, a star aromatic compound, is commonly found in
fluorescence molecules and used to synthesize stable
optoelectronic materials. Reason for the wide application of
carbazole-based polymers is owing to their excellent thermal
and photochemical stability, outstanding hole transporting
E-mail: wxt@fjirsm.ac.cn
University of the Chinese Academy of Sciences, Beijing, 100049, China.
b.
Electronic Supplementary Information (ESI) available: Selected bond lengths and
angles, PXRD curve, TGA curve, IR spectra, CCDC-1527984 for TCZ-001, CCDC-
1
527985 for TCZ-002, CCDC-1527986 for TCZ-003, CCDC-1527987 for TCZ-004,
CCDC-1527988 for TCZ-005. For ESI and crystallographic data in CIF or other
electronic format see DOI: 10.1039/x0xx00000x.
33,34
ability and large conjugated π system.
Carbazole could be
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 1
Please do not adjust margins

PleaseC dr oy sn t oE tn ag dCj uo smt mm argins
Page 2 of 12
ARTICLE
Journal Name
functionalized at (3,6-), (2,7-) , or N positions. 2, 7-carbazole- EL-Cube Element Analyzer. Powder X-ray diffraVciteiwoAnrtic(lPe XORnlDine)
based polymers have lower band gap and better fluorescent data were collected on a Rigaku MiniFleDxOI6: 1000.10d3if9f/rCa7cCtEo0m03e6t1eGr
property, and functionalized at N positions is beneficial to self- using Cu Kα radiation (λ = 0.154 nm). Infrared spectra were
3
5-38
-1
assembling of the porous structure.
Considering these recorded with KBr pellets in the range 4000-400cm on a
Spectrum One FT-IR spectrometer.
properties of carbazole-based polymers, 2,7-bis(4-benzoic Perkin-Elmer
acid)-N-(4-benzoic acid) carbazole (H3L27) was designed and Thermogravimetric analysis (TGA) experiments were carried
synthesized based on the fact that the appended benzoic acid out on a NETZSCH STA 449C Jupiter thermogravimetric
3
9-47
moieties will significantly increase the size of the ligand.
analyzer in flowing nitrogen with the sample heated in an
o
Due to the nature of H3L , a conjugated tricarboxylic acid Al O crucible from room temperature to 1000 C at a heating
27
2 3
II
II
−1
ligand, its reaction with Zn and Cd salts was predicted to rate of 10 K min . Metal elemental analyses (for Zn, Ni and Eu)
form 1D to 3D structure coordination polymer based on were performed with a HORIBA Jobin Yvon Ultima2 Inductively
different metal clusters nodes. Herein, we present five CPs, Coupled Plasma OES spectrometer (ICP).
[
(
[
Zn3(L27) (DMA) (H O) ]
(
TCZ-001), [Zn3(L27) (DMA) (EtOH) ]
4,4’-Dibromo-2-nitrobiphenyl(1):
Compound
1
was
4,4’-
2
6
2
4 n
2
6
2 n
4
2
TCZ-002),
[Zn3(L27) (DMA) (CH OH)]
(TCZ-003), synthesized followed the reported procedure.
2
6
3
n
Cd3(L27) (DMA) (H O) ]
(TCZ-004),
[Cd9(L27) DMA (4,4’- dibromobiphenyl (20.0 g, 64.1 mmol) was dissolved in glacial
6 13
2
6
2
2 n
BPY) (OH) (H O) ]
(TCZ-005
)
(DMA
=
N,N- acetic acid (300 mL), and the mixture was stirred and heated
2
2
2
13.5 n
dimethylacetamide, 4,4’-BPY = 4,4'-bipyridine, TCZ= “T”-shape to 110 °C. When 4,4’-Dibromobiphenyl was dissolved totally,
carbazole-based polymers).
fuming concentrated nitric acid (95%, 80 mL) was added slowly
to the solution. Then, heating the mixture at 110 °C until the
precipitate formed after adding fuming concentrated nitric
acid was redissolved. The solution was cooled to room
temperature and the resulting solid was collected by filtration.
Experimental section
Materials and Methods
After
recrystallisation
from
EtOH,
4,4’-Dibromo-2-
4
,4’-dibromobiphenyl, potassium tert-butoxide, ethyl 4-
nitrobiphenyl was obtained as a yellow solid (20.8 g, 91% yield).
fluorobenzoate, potassium carbonate, tetrakis(triphenylphosp-
hine)palladium(0), Zn(NO ) ·6H O, Cd(NO ) ·6H O and solvents
1
H NMR (400 MHz, CDCl ): δ (ppm) = 8.05 (d, J = 1.96 Hz, 1 H),
3
3
2
2
3 2
2
7
.78 (dd, J = 6.24, 2.00 Hz, 1 H), 7.78 (d, J = 8.44 Hz, 2 H), 7.31
were purchased commercially and used directly. Elemental
analyses (C, H and N) were performed with an Elementar Vario
13
(d, J = 8.28 Hz, 1H), 7.18 (d, J = 8.40 Hz, 2 H). C NMR (400
MHz, CDCl ): δ (ppm) = 149.23, 135.60, 135.30, 134.14, 133.04,
3
3 27
Scheme 1. Synthesis of 2, 7-bis(4-benzoic acid)-N-(4-benzoic acid) carbazole (H L )
2
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 3 of 12
PleaseC dr oy sn t oE tn ag dCj uo smt mm argins
Journal Name
ARTICLE
1
32.05, 129.42, 127.29, 123.09, 121.85. MS (EI): calculated for 130.08, 126.52, 124.16, 122.02, 121.60, 113.03, 61.43, 14.30.
View Article Online
DOI: 10.1039/C7CE00361G
C H Br NO m/z: 357.00, found m/z: 356.90.
MS (EI): calculated for C H Br NO m/z: 473.16, found m/z:
21 15 2 2
12
7
2
2
2
,7-Dibromocarbazole(2): Compound
2
was synthesized 473.06
followed the reported procedure. A solution of (10 g, 28.0 2,7-bis(4-methyl benzoate)-N-(4-ethyl benzoate) carbazole
mmol) in phosphorous acid triethyl ester (35 ml) was heated to (4): A solution of Methyl 4-boronobenzoate (2.17 g, 12 mmol)
50°C in an inert atmosphere. The system was allowed to and K CO (38.8 g, 0.28 mol) in 1:1 EtOH/H O (80 ml) was
42
1
1
2
3
2
react for 18 h and a brown solution was obtained. The solvents added to a solution of 2,7-Dibromo-N-(4-methyl benzoate)
were removed by vacuum distillation and the product was carbazole (2.51 g, 5.3 mmol) in toluene (80 ml). The reaction
purified by column chromatography with petroleum was stirred for 20 min and then tetrakis(triphenylphosphine)
ether/ethyl acetate (10:1, v/v) as the eluent. The title palladium(0) (0.30 g, 0.26 mmol) was added as catalyst. The
compound was obtained as white crystal (4.82 g, 53% yield). suspension was refluxed under nitrogen for 5 days. The
1
H NMR (400 MHz, acetone- d ): δ (ppm) = 10.63 (s, 1 H), 8.06 reaction mixture was allowed to cool to room temperature
6
(
6
1
d, J = 8.36 Hz, 2 H), 7.74 (d, J = 1.52 Hz, 2 H), 7.36 (dd, J = 1.56, and the solid in the reaction mixture was removed by filtration.
13
.76 Hz, 2 H). C NMR (400 MHz, acetone- d ): δ (ppm) = The filtrate was extracted with ethyl acetate and the solvent in
6
41.12, 122.43, 121.75, 121.61, 119.10, 114.04. MS (EI): the collected organics was removed under reduced pressure.
calculated for C H Br N m/z: 325.00, found m/z: 325.10.
After recrystallization from ethanol, 2,7-bis(4-methyl
12
7
2
2
,7-Dibromo-N-(4-ethyl benzoate) carbazole (3): Potassium benzoate)-N-(4-methyl benzoate) carbazole was obtained as
1
tert-butoxide (3.36 g, 30 mmol) and 2,7-Dibromocarbazole white solid (1.98 g, yield 64%). H NMR (400 MHz, DMSO-d ) δ
6
(9.78 g, 30 mmol) were dissolved in dry DMF (300 mL) in a (ppm) = 8.41 (d, J = 8.2 Hz, 2 H), 8.29 (d，J = 8.5 Hz,2 H),8.04
two-necked flask fitted with a magnetic stirrer and condenser. (d, J = 8.4 Hz,4 H), 7.98 (d, J = 8.5 Hz, 2 H), 7.90(d, J = 8.3 Hz, 4
Under an atmosphere of nitrogen, the solution was stirred at H), 7.72 (d, J = 9.3 Hz, 2 H), 7.60 (dd, J = 2.8, 5.6 Hz, 2 H), 4.34
o
13
1
10 C for 60 min and then ethyl 4-fluorobenzoate (6.10 ml, 33 (d, J = 7.1 Hz,2 H), 2.81 (s, 2 H) 1.34 (d, J = 7.1 Hz,3 H). C NMR
mmol) was added. The system was allowed to react for 24 h (400 MHz, DMSO-d ) δ (ppm) = 166.06, 162.78, 145.69, 141.16,
6
and an apricot solution was obtained. The solvents were then 140.01, 137.89, 131.83, 130.32, 129.36, 128.31, 127.76, 127.26,
removed by vacuum distillation. The crude residue was 126.21, 123.53, 121.86, 108.62, 61.21, 36.25, 31.23, 14.67. MS
recrystallized from ethanol (50 ml). A white powder was (EI): calculated for C H 9NO m/z: 583.64, found m/z: 583.63.
3
7
2
6
1
obtained (10.7 g, 88.6% yield). H NMR (400 MHz, CDCl ) δ
2,7-bis(4-benzoic acid)-N-(4-benzoic acid) carbazole (H L ):
3 27
3
(
ppm) = 8.35 (d, J = 8.5 Hz, 2H), 7.97 (d, J= 8.3 Hz, 2H), 7.64 (d, A solution of NaOH (1.20 g, 30 mmol) in H O (15 ml) was
2
J = 8.5 Hz, 2H), 7.56 (d, J = 1.56 Hz, 2H), 7.45 (dd, J = 1.6, 6.7 Hz, added in a suspension of 2,7-bis(4-methyl benzoate)-N--(4-
1
3
2
H), 4.49 (q, J = 7.1 Hz, 2H), 1.48 (t, J = 7.1 Hz, 3H). C NMR methyl benzoate) carbazole (1.98 g, 3.39 mmol) in 1:1
(
400 MHz, CDCl ) δ (ppm) = 165.64, 141.30, 140.50, 131.67, methanol/tetrahydrofuran (15 ml). The mixture was stirred at
3
Table 1 Crystal and X-ray experimental data for compounds TCZ-001
–
TCZ-005
TCZ-003
Compound
Empirical formula
Formula weight
Crystal system
Space group
a(Å)
TCZ-001
TCZ-002
TCZ-004
TCZ-005
C
90
H98N8O22Zn
3
C
94 102
H N
8
O20Zn
3
C
91
H
N
94 8
O19Zn
3
C
90
H94Cd
3
N
8
O
20
278 9 25 66.5
C H284Cd N O
1839.87
Triclinic
P-1
1860.02
1799.85
Triclinic
P-1
972.47
Triclinic
P-1
6051.04
Monoclinic
C2/c
Monoclinic
Pn
14.6832(5)
15.5902(6)
19.3560(3)
83.727(5)
81.479(5)
87.507(6)
4354.0(2)
2
30.057(6)
16.187(3)
21.894(4)
90
14.8042(4)
16.9788(4)
17.5636(6)
99.169(2)
104.186(3)
101.157(2)
4098.8(2)
2
11.151(4)
14.724(5)
15.569(5)
63.180(12)
71.118(14)
79.302(17)
15.8325(19)
22.884(3)
36.596(5)
90
b(Å)
c(Å)
α(°)
β(°)
114.478(3)
90
97.523(2)
90
γ(°)
3
V(Å )
9695(3)
4
2156.1(12)
13145(3)
2
Z
2
Temperature(K)
293(2)
293(2)
1.274
293(2)
293(2)
1.498
0.809
994
293(2)
1.509
-
3
D
c
(Mg m )
1.403
1.458
-
1
μ(mm )
0.898
0.784
1.672
0.799
F(000)
1920
2912
1876
6094
a
1
R
,wR2b(I>2σ(I))
0.0780,0.2223
2.00 to 27.45
-17 to 19
0.0495,0.1450
2.25 to 27.48
-32 to 38
0.0736, 0.2125
3.36 to 74.66
-18 to 17
0.0429,0.1379
2.11 to 27.52
-14 to 14
0.0519,0.1315
2.20 to 27.51
-20 to 20
θ
range(deg)
h,k,l ranges
-
-
20 to 19
25 to 25
-21 to 20
-21 to 14
-16 to 19
-29 to 29
-28 to 28
-21 to 21
-19 to 20
-47 to 47
GOF on F2
1.020
1.089
1.099
1.048
1.107
a
b
2
O
2
C
2
2
0
2
1/2
R = ∑||F
O
| - F
C
||/∑|F
0
|. wR
2
= [P[w(F
- F
) ]/∑[(F
) ]]
.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 3
Please do not adjust margins

PleaseC dr oy sn t oE tn ag dCj uo smt mm argins
Page 4 of 12
ARTICLE
Journal Name
o
5
(
0 C for overnight and then it was added to a solution of HCl Single-Crystal Structure Determination.
View Article Online
DOI: 10.1039/C7CE00361G
300 ml, pH= 2). After stirring for 10min, sediment was
collected by filtration. Washed with tetrahydrofuran and ether
and then allowed to dry under reduced pressure, a beige solid
was obtained (1.70 g, yield 95%). H NMR (400 MHz, DMSO-d )
δ (ppm) = 8.45 (d, J = 8.1 Hz, 2 H), 8.28 (d
d, J = 8.4 Hz, 4 H), 7.95 (d, J = 8.5 Hz, 2 H), 7.89 (d, J = 8.4 Hz, 4
H), 7.74 (d, J = 8.9 Hz, 2 H), 7.62 (dd, J = 7.0, 12.1 Hz, 2 H).
NMR (400 MHz, DMSO-d ) δ (ppm) = 167.64, 167.21, 145.28,
The X-ray single-crystal structure analyses for the TCZ-001
,
TCZ-002
24HG CCD diffractometer (Mo Kα radiation λ=0.71073Å
graphite-monochromator at 293(2) K. TCZ-003 was
, TCZ-004, TCZ-005 were collected on a Rigaku Saturn
7
1
6
)
，J = 8.5 Hz, 2 H),8.03
performed on a SuperNova, Dual, Cu at zero, Atlas
diffractometer equipped with graphite-monochromated Cu Ka
radiation (λ= 1.54184 Å) at 293(2) K. All of the structure were
solved by direct methods and refined by full matrix least-
(
1
3
C
6
1
1
41.41, 140.89, 138.31, 132.00, 130.45, 129.97, 129.30, 127.75,
27.23, 123.18, 122.07, 120.71, 108.66. MS (EI): calculated for
C H NO m/z: 526.14, found m/z: 526.13.
2
48
squares of F using the SHELX-97 program. Hydrogen atoms
were added in idealized positions. The SQUEEZE routine of the
PLATON software suite was used in removing highly
disordered solvent molecules in TCZ-002 and TCZ-005. The
final formulas were calculated according to the Squeeze
33
21
6
Synthesis of [Zn (L ) (DMA) (H O) ] (TCZ-001)
3
27 2
6
2
4 n
Solvothermal reaction of Zn(NO ) ·6H O (59.5 mg, 0.2 mmol),
,7-bis(4-benzoic acid)-N-(4-benzoic acid) carbazole (H3L27
26.3 mg, 0.05 mmol) in the mixture of N,N′-
dimethylacetamine (DMA) (1.5 ml) and H O (0.5 ml) at 353 K
for 72 h gave rise to colorless prism crystals of TCZ-001 (18.5
mg, Yield: 40.3%). Anal. Calcd (%) for C H N O Zn : C 58.75,
H 5.36, N 6.09. Found: C 58.93, H 5.12, N 5.99.
Synthesis of [Zn (L ) (DMA) (CH CH OH) ] (TCZ-002)
3
2
2
results combined with the results from elemental analyses and
2
(
)
49,50
thermogravimetric analysis (TGA).
Crystal data for TCZ-001
-
TCZ-005 are presented in Table 1. Selected bond lengths and
2
angles of TCZ-001
– TCZ-005 are listed in Table S1 of
Supporting Information.
Experiments of metal ion sensing
9
0
98
8
22
3
The finely ground powder samples (3 mg, respectively)
immersed in 3 mL DMA, H O or ethanol solutions of M(NO ) .
3
27 2
6
3
2
2 n
2
3 x
Solvothermal reaction of Zn(NO ) ·6H O (59.5 mg, 0.2 mmol),
,7-bis(4-benzoic acid)-N-(4-benzoic acid) carbazole (H3L27
26.3 mg, 0.05 mmol) in the mixture of N,N′-
dimethylacetamine (DMA) (1.5 ml) and ethanol (0.5 ml) at 353
K for 72 h gave rise to apricot bulk crystals of TCZ-002 (22.1 mg,
Yield: 47.6%). Anal. Calcd (%) for C H N O Zn : C 60.70, H
.53, N 6.02. Found: C 60.08, H 5.61, N 6.07.
Synthesis of [Zn (L ) (DMA) (CH OH)] (TCZ-003)
3
2
2
Suspension solutions were obtained after preparation by an
ultrasound method for 3 hours at room temperature. And then,
the luminescence emission spectra of the suspension solutions
were measured immediately under excitation at 370nm. The
data were obtained from two measurements on independent
luminescence sensing experiments.
2
(
)
94
102
8
20
3
5
Photophysical measurements
3
27 2
6
3
n
The solid-state and suspension solutions luminescence
emission/excitation spectra and solid-state luminescence
lifetimes were recorded on an Edingburgh Insruments FLS980
fluorescence spectrophotometer. The quantum yields of the
solid-state samples were determined by an absolute method
using an integrating sphere on an Edingburgh Insruments
FLS920 spectrometer. The lifetimes of the solid-state samples
were acquired on an Edinburgh Analytical FLS920 instrument
with a Picoseconds Laser Diode.
Solvothermal reaction of Zn(NO ) ·6H O (59.5 mg, 0.2 mmol),
3
2
2
2
(
,7-bis(4-benzoic acid)-N-(4-benzoic acid) carbazole (H3L27
26.3 mg, 0.05 mmol) in the mixture of N,N′-
dimethylacetamine (DMA) (1.5 ml) and methanol (0.5 ml) at
53 K for 72 h gave rise to colorless bulk crystals of TCZ-003
23.7 mg, Yield: 52.7%). Anal. Calcd (%) for C H N O Zn : C
)
3
(
9
1
94
8
19
3
6
0.72, H 5.26, N 6.22. Found: C 59.92, H 5.11, N 6.03.
Synthesis of [Cd (L ) (DMA) (H O) ] (TCZ-004)
3
27 2
6
2
2 n
Solvothermal reaction of Cd(NO ) ·6H O (61.7 mg, 0.2 mmol),
3
2
2
2
,7-bis(4-benzoic acid)-N-(4-benzoic acid) carbazole (H3L27
)
(26.3 mg, 0.05 mmol) in the mixture of N,N′-
dimethylacetamine (DMA) (1.5 ml) and 10:1 ethanol/H O (0.5
2
ml) at 373 K for 96 h gave rise to colorless bulk crystals of TCZ-
0
04 (15.3 mg, Yield: 31.5%). Anal. Calcd (%) for C H N O Cd :
90 94 8 20 3
C 55.57, H 4.87, N 5.76. Found: C 55.31, H 4.81, N 5.61.
Synthesis of [Cd (L ) DMA (4,4’-BPY) (OH) (H O) ] (TCZ-
9
27 6
13
2
2
2
13.5 n
0
05).
The synthesis of TCZ-005 was carried out by heating a solution
mixture of 2,7-bis(4-benzoic acid)-N-(4-benzoic acid) carbazole
H3L27) (26.3 mg, 0.05 mmol), 4,4'-bipyridine (7.8 mg, 0.05
mmol) and Cd(NO ) ·6H O (61.7 mg, 0.2 mmol) in N,N′-
(
3
2
2
dimethylacetamine (DMA) (1.5 ml) and H O (0.5 ml) at 353 K
for 72 h. Daffodil prism crystals of TCZ-005 were obtained (47
2
Fig.
1 (a) View of the 1D infinite chain in TCZ-001; (b) Topological
representation of the chain in TCZ-001 (ligand L27 are marked as yellow balls;
metal nodes are marked as plum ball.
mg, Yield: 48 %). Anal. Calcd (%) for C556H552N O Cd : C
50
124
18
5
5.92, H 4.66, N 5.86. Found: C 55.41, H 4.62, N 5.63.
4
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 5 of 12
PleaseC dr oy sn t oE tn ag dCj uo smt mm argins
Journal Name
ARTICLE
Results and discussion
View Article Online
DOI: 10.1039/C7CE00361G
Crystal structure of TCZ-001
Single crystal X-ray diffraction analysis indicates that TCZ-001
̅
crystallizes in the triclinic 푃1 space group. Structural analysis of
TCZ-001 shows that it is one-dimensional (1D) two-connected-
chained structure. The T-shape L27 ligand is connected by
II
II
dinuclear Zn cluster and mononuclear Zn ion which
coordinated on one of the two connected chains respectively
(
II
II
Fig 1a). The dinuclear Zn cluster contains two types of Zn ion
in different coordination modes (Fig. S1b). One of the two
II
types of Zn (1) is coordinated to three O atoms from the
carboxylate group of three L27 ligands and an O atom from a
II
water molecule. The other one Zn (3) is coordinated to three O
atoms from the carboxylate group of same three L27 ligands
and it is coordinated to three O atoms from three water
molecules at the same time. In the meantime, it is the key for
forming crystal that forming hydrogen bond between H atoms
Fig.
3
(a) View of the 1D infinite chain in TCZ-003; (b) Topological
representation of the chain in TCZ-003 (ligand L27 are regarded as pink balls;
metal nodes are marked as yellow ball).
of coordinated water molecules and O atoms belonged to
II
II
other chains. The mononuclear Zn (2) ion on the other chain is group. A typical trinuclear Zn cluster is connected by L27
five-connected with oxygen atoms of carboxylate group from ligands and a three-dimensional (3D) porous structure is
three L27 ligands and the last coordination position is occupied obtained. The asymmetric unit possesses one L27 ligands, half
by a DMA molecule (Fig. S1a). As summarized in Table S1, the of a three Zn cluster and a DMA molecule. The Zn cluster
Zn-O bond lengths of TCZ-001 range from 1.926(3) Å to consists of two tetrahedral Zn ions [Zn (2), Zn (2’)] and an
II
II
II
II
II
II
II
II
2
.193(3) Å.
A PLATON calculation indicated that the total potential six carboxyl oxygen atoms of six L27 ligands. Both Zn (2) and
octahedral Zn ion [Zn (1)] (Fig 2a). Zn (1) is six-coordinated by
II
II
solvent volume when the DMA molecules are removed is Zn (2’) are bonded to
a DMA molecule and three
3
3
II
1
711.8 Å , which corresponds to 39.30% (4354.0 Å ) totally bismonodentate carboxylates, which are also bonded to Zn (1).
II
II
II
volume. Topologically, dinuclear Zn cluster , mononuclear Zn
The Zn (1)-O bond lengths vary from 2.0198(17) Å to 2.094(2)
II
ion and L27 ligands are regarded as 3-connected nodes, the Å and the Zn (2)/(2’)-O bond lengths range from 1.9455(19) Å
2
network of TCZ-001 is classified as 3-connected uninodal {4 .6} to 1.997(2) Å. A 1D channel in TCZ-002 has a diameter of 7.4 Å
3
topology (Fig. 1b).
and the solvent-accessible volume is 1074.0 Å , which is 44.3%
of per unit cell volume (2423.8 Å ) as calculated by PLATON
Fig 2b, 2c). According to the data of TGA from 303 K to 413 K,
3
Crystal structure of TCZ-002
(
Structural analysis according to single crystal X-ray diffraction free solvent molecules occupy 24% of total weight of TCZ-002
indicates TCZ-002 crystallizes in the monoclinic C2/c space
.
Fig. 4 (a) Secondary building units (SBUs) of TCZ-004; (b) 2D structure of
Fig. 2 (a) Secondary building units (SBUs) of TCZ-002; (b) 3D framework of TCZ-
02 having a diameter of 7.4 Å; (c) View of 1D channel indicated by a yellow
cylinder; (d) Schematic view of the 3,6-connected network in TCZ-002.
TCZ-004 viewed down the c-axis with a 11.6 x 8.36
space-filling version of the 2D network of TCZ-004. (d) Topological
representation of the 3,6-connected network in TCZ-004
Å channel. (c) A
0
.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 5
Please do not adjust margins

PleaseC dr oy sn t oE tn ag dCj uo smt mm argins
Page 6 of 12
ARTICLE
Journal Name
And there are ca.238 electron count voids and 1090 total including an O atom from a carboxyl group which is the bridge
View Article Online
II
II
II
II
DOI: 10.1039/C7CE00361G
potential solvent accessible void volume in per unit cell as between Zn (1) and Zn (3). Zn (3) and Zn (2) are bridged by
II
calculated by PLATON. So it can be figured out that there are three carboxyl groups of L27 ligands (Fig. S2). In addition, Zn (3)
II
three and a half DMA molecules and two ethanol molecules is coordinated with a methanol molecule and Zn (2) is
II
per unit cell. From a topological point of view, the Zn cluster coordinated with a DMA molecule. The Zn-O bond distances
could be regard as 6-connected node and the L27 ligands could are range from 1.933(4) Å to 2.049(4) Å. The solvent-accessible
3
3
be regard as 3-connected node. TOPOS analysis based on that volume is 30.90% (1265.6 Å /4098.8Å ) as calculated by
view reveals that the 3D structure of TCZ-002 can be PLATON when the solvent molecules are removed. The
rationalized to a 3,6-connected net with a point symbol of structure of TCZ-003 can be described as a 3, 6-connected
2
.
4. 2. 7.
2
11 4 .
3
{
4 6} {4 6 8 10 } (Fig 2d).
network with a Schläfli symbol of {4 .6 } {4 } when each
2
2
II
twisty trinuclear Zn cluster is regarded as 6-connected node
and each L27 ligand is reduced as a 3-connected node by
Crystal structure of TCZ-003
Single crystal X-ray diffraction analysis proves that TCZ-003 TOPOS software (Fig. 3b).
̅
crystallizes in the triclinic 푃1 space group and it is also 1D
structure, however, which is different from the 1D structure of
Crystal structure of TCZ-004
TCZ-001. The difference in the structure between TCZ-003 and According to single crystal X-ray diffraction analysis, TCZ-004
TCZ-001 is that TCZ-003 is 1D four-connected-chained possesses a two-fold two-dimensional (2D) network that
II
̅
structure and the L27 ligands are connected by trinuclear Zn
crystallizes in the triclinic 푃1 space group. The framework is
II
clusters (Fig. 3a). Meanwhile, the asymmetric unit of TCZ-003 electrically neutral and contains a linear three-Cd cluster
consists of a trinuclear Zn cluster, two L27 ligands, six DMA connected by sixteen carboxylate oxygens of six L27 ligands and
molecules and a coordinated methanol molecules. Zn (1) of four DMA molecules (Fig. 4a, 4b, 4c). In the linear three-Cd
the trinuclear Zn clusters are four coordinated with O atoms cluster, Cd (2) and Cd (2’) are six connected by O atoms from
II
II
II
II
II
II
II
from three carboxyl groups of L27 ligands and a DMA molecules, three L27 ligands and a DMA molecule. Similar to Cd (2) and
Fig. 5 (b) View of the 1D infinite chain in TCZ-005 down the b-axis and (a), (d), (c) are the view of parts of TCZ-005 down the c-axis. (e) Topological
representation of the chain in TCZ-005
.
6
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 7 of 12
PleaseC dr oy sn t oE tn ag dCj uo smt mm argins
Journal Name
ARTICLE
II
II
Cd (2’), Cd (1) is also six coordinated with O atoms, but which
are from four L27 ligands and two DMA molecules. The range of
Cd-O bond lengths is from 2.167(2) Å to 2.376(3) Å and the
void volume calculated by PLATON is 22.1% of total volume of
View Article Online
DOI: 10.1039/C7CE00361G
II
the framework. Topologically, the linear three-Cd cluster can
be viewed as a 6-connected node, therefore, the network of
TCZ-004 belong to a 3,6-connected net with a Schläfli symbol
3
6
6
3
of {4 } .{4 .6 .8 } (Fig. 4d).
2
Crystal structure of TCZ-005
Single-crystal X-ray diffraction of TCZ-005 revealed that the
framework belong to the Monoclinic Pn space group and the
II
huge asymmetric unit consists of nine Cd ions, six L27 ligands,
thirteen DMA molecules, two 4,4'-Bipyridine molecules,
thirteen and a half H O molecules and two hydroxide ions.
2
TCZ-005 is composed of three types of parallel 1D structure
Fig. 6 Solid-state emission spectra of TCZ-001 to TCZ-005.
chains (Fig. 5b). Two types of the chains are formed by
II
connecting mononuclear Cd ion with L27 ligands and both of
2
with a Schläfli symbol of {4 .6} and the chains connected by
them are bridged by 4,4'-bipyridine molecules(Fig. 5c). The
2.
3.
2.
II
4,4'-Bipyridine has a point (Schläfli) symbol {4 6 8}{4 6} . The
structure of TCZ-005 could be described as a SP 1-periodic net
4,4)(0,2) in the 1D_2D.ttd database (Fig. 5e).
3
other type of chain consists of dinuclear Cd cluster connected
by L27 ligands and forming hydrogen bond between H atoms of
coordinated water molecules and O atoms belonged to other
chains results in the growth of the crystal (Fig. 5a). The Cd-O
bond distances are range from 2.169(4) Å to 2.631(6) Å and
Cd-N bond distances are from 2.295(7) Å to 2.321(5) Å which
are shown in Table S1. The solvent-accessible volume is 28.70%
as calculated by PLATON, which is limited as part of the
channels of TCZ-005 are occupied by [Cd(OH) (DMA) (4,4'-
(
X-ray powder diffraction and thermal analysis
Powder X-ray diffraction (PXRD) for the bulk samples of TCZ-
0
0
01
– TCZ-005 were carried out at room temperature. For TCZ-
01 to TCZ-005, the experimental PXRD patterns correspond
well with the simulated from the data of single crystal X-ray
diffraction and are shown in Fig. S3. To estimate the thermal
stability, thermogravimetric analysis (TGA) experiments were
2
2
Bipyridine)(H O)] cluster (Fig. 5d). Topologically, the chains
2
II
consists of dinuclear Cd cluster belong to 3-connected net
2
+
Fig. 7 (2a) and (b) Emission spectra of TCZ-001 in DMA solution upon the addition of various concentrations of Ni ; (c) CIE chromaticity diagram showing
+
the Ni concentration-dependent luminescence colour change of TCZ-001 in DMA solution under the excitation at 370nm.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 7
Please do not adjust margins

PleaseC dr oy sn t oE tn ag dCj uo smt mm argins
Page 8 of 12
ARTICLE
Journal Name
performed on polycrystalline samples of TCZ-001 to TCZ-005 generate a 3D structure and we speculated that a rigid non-
View Article Online
II
o
-1
DOI: 10.1039/C7CE00361G
under a N atmosphere with a heating rate of 10 C min in planar arrangement due to the coordination of Zn caused the
2
o
the range of 30-800 C. For TCZ-001, a weight loss of 23.5% quenching in emission. The structure of TCZ-003 is also 1D
from room temperature to 140 C is ascribed to the loss of free chain but it is different in emission intensity between TCZ-001
o
o
DMA molecules (calc. 23.6%). From 150 to 400 C, coordinated and TCZ-003 may be due to the varying degree of planarity
,
DMA and water molecules were removed generally with a which will impact the symmetry and the allowance of the
weight loss of 9.8% (calc. 8.7%). The frame work collapses and lowest energy electronic transitions. In TCZ-004, the structure
o
decomposes after 420 C. Similar to TCZ-001, the curves of could be regard as a 2D network. And the degree of planarity
5
1,55,59,63-67
TCZ-002 to TCZ-005 display weight losses of 23.8%, 20.1%, 19.9% in TCZ-004 is better than TCZ-002 and TCZ-003
.
and 18.4%, respectively, corresponding to the removal of
guest DMA, water, ethanol or methanol molecules (calc. 23.6%,
Metal ion sensing
1
9.4%, 19.7% and 16.0%). The coordinated DMA, water The intense blue luminescence of TCZ-001 promotes us to
molecules or methanol molecules were removed slowly from investigate its application in sensing metal ions. The finely
o
1
50 to 370 C. Upon further heating, the TG curves of TCZ-004 ground powder samples (3 mg, respectively) of TCZ-001
II
and TCZ-005, which assembled from L27 ligands and Cd ions, immersed in 3 mL DMA, H O or EtOH solutions of M(NO ) .
2
3 x
o
display rapid weight losses from 380 to 420 C. Comparing to Suspension solutions were obtained after preparation by an
TCZ-004 and TCZ-005 in the TG curve, TCZ-001 TCZ-002 and ultrasound method for 3 hours at room temperature. Although
TCZ-003, which contain Zn ions, are more stable and the several variations appeared in these suspension solutions, only
,
II
o
2+
weight losses are observed from 420 to 495 C. All of the TGA in solution of Ni ions did a remarkable change occur in the
curves are shown in Fig. S4.
emission spectra. The emission spectra of the suspension
solutions are shown in Fig. S6. A remarkable red shift in the
emission spectra of suspension solution containing Ni can be
Photoluminescence properties
2+
The photoluminescence properties of TCZ-001 to TCZ-005 and noticed and the distance of the red shift depends on the
2+
H3L27 ligand were investigated under room temperature. The concentration of Ni ions in the suspension solution.
free solid-state H3L27 ligand show a blue fluorescent emission Keeping this in mind, a series of TCZ-001 suspension
band at 459 nm under 375 nm wavelength excitation, which is solution containing different concentration of Ni ion were
2+
5
1-58
probably due to π* → n or π* → π transitions.
excitation at 370 nm, the solid-state emission spectra of TCZ- main emission peak was gradually moved as the Ni
01 to TCZ-005 display intense emission bands centered at 435 concentration increased which can be utilized in selective
Under designed and prepared. As shown in Fig. 7a and Fig. 7b, the
2+
0
2+
nm, 435 nm, 430 nm, 438 nm and 500 nm respectively. The sensing of Ni ions. To facilitate the application of TCZ-001
,
2+
blue shifts of TCZ-001 to TCZ-004 are tentatively assigned the Ni ions concentration-dependent spectra have been
strong electrostatic interaction between the L27 ligands and transformed into the Commission Internationale de L’Eclairage
metal ions by donation of the lone pair electrons of O atoms to (CIE) 1931 coordinates and the locus are drawn in the CIE
51,57,61
68,69
the empty orbitals of the metal ions.
TCZ-001 to TCZ-004 are neither metal-to-ligand charge transfer
MLCT) nor ligand-to-metal charge transfer (LMCT) in nature
The emissions of system according to the CIE coordinates (Fig. 7c).
The
(
II
II
since Zn /Cd ions are difficult to oxidize or to reduce due to
their d configurations. For TCZ-005, the emission may exist as
10
a mixture characteristic of intraligand and ligand-to-
II
ligand charge transitions (LLCT), since the Cd ions are
1
0
difficult to oxidize or reduce due to their d
configurations.
5
1,52,58,61,62
The emission decay lifetimes of
TCZ-001 to TCZ-005 were found to be τTCZ-001 = 2.690 ns, τTCZ-002
=
6
3
4.352 ns, τTCZ-003 = 3.453 ns, τTCZ-004 = 2.572 ns and τTCZ-005
4.16 ns. And the emission decay lifetimes of H3L27 was τH3L27
=
=
.78 ns. The external quantum yield (Φ ) of TCZ-001 is as high
F
as 25.95%, a remarkable enhancement of the luminescent
quantum yield compared with the solid-state emission of H3L27
(
Φ = 14.3%). However, the external quantum yields of TCZ-002
F
to TCZ-005 were found to be 2.52%, 8.41%, 13.28% and
1.51%, respectively, which were similar or lower than the
1
external quantum yield of the ligand. The different
fluorescence intensity for TCZ-001 to TCZ-004 is probably due
to the different structure of these CPs. In TCZ-001, simple 1D
polymer chains were confined through hydrogen-bonding
interactions and the L27 ligands were in a planar arrangement.
Fig. 8 The locus of TCZ-003 in CIE chromaticity diagram showing the
relationship between luminescence colour and the Ni concentration.
2+
While in TCZ-002, L27 ligands were connected together to
8
| J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 9 of 12
PleaseC dr oy sn t oE tn ag dCj uo smt mm argins
Journal Name
ARTICLE
coordinates in CIE 1931 are calculated by the ratio between state emission of the flocculent precipitate is between 430-
View Article Online
DOI: 10.1039/C7CE00361G
red, green and blue according to emission spectra and it would 650nm.(Fig. S8) Thus, we speculate that the emissions
2
+
not be disturbed by the intensity of the excitation light between 390 nm to 500 nm are assigned to the CPs with Zn
70,71
source.
excitation light source or the slit width of the fluorescence the CPs with mixture metal nodes including Zn and Ni .
spectrometer, can be limited in course of measurement. There is a remarkable relationship between the intensity ratios,
Thus, the errors, caused by the intensity of the nodes and the emissions between 430 nm to 600 nm belong to
2+
2+
With the intention to figure out the reason to the which is of emissions (390 - 500 nm) to emissions (430 – 600
measurement, particles in suspension solutions were nm), and percentage composition of the CPs with mixture
2+
2+
separated by centrifugal separation and washed by DMA. After metal nodes including Zn and Ni . With the increasing of the
2+
2+
filtering and drying at room temperature, pale green powders CPs with mixture metal nodes including Zn and Ni , part of
were obtained. The Inductively Coupled Plasma OES the emissions (390 – 500nm) was absorbed by the CPs with
2+
2+
spectrometer (ICP) data of the pale green powders showed mixture metal nodes including Zn and Ni as excitation light.
2
+
2+
that a partly replacement of Zn ions in TCZ-001 by Ni ions. Meanwhile the percentage compositions of the CPs with
2+
2+
2+
(
Fig. S7a) Divalent Ni cations, which show coordination mixture metal nodes including Zn and Ni much depend on
environment similar to that of Zn , may replace partial Zn
2+
2+
2+
72-77
the concentration of Ni during the measurement.
cations during the pre-treatment. Moreover, the partial Because transmetalation occurred with increasingly
2+
replacement of the Zn was attributed to the strong concentrated exchange solutions, and less concentrated
2+ 72-75
coordinate ability of Ni .
And the structure of TCZ-001 solutions resulted in exclusively metal sorption, there is
after measurement is similar to that before measurement, evidence that the concentration of the metal ions in the
7
2
which were monitored by the powder X-ray diffraction (PXRD) exchange solutions is crucial.
2+
(Fig. S7b). In addition, replacing Zn(NO3)2 by Ni(NO3)2 in
The measurement of Ni concentration by TCZ-001 can also
synthesizing TCZ-001, light green flocculent precipitate was be used in water or ethanol solution (Fig. S9). But the
obtained after solvothermal reaction. Although single crystal measurement resolution of TCZ-001 in H O or ethanol solution
2
cannot be obtained, PXRD show the structure of the flocculent was not as good as that in DMA solution. It might be attributed
precipitate similar to the structure of TCZ-001. And the solid- to the impact to structure of TCZ-001, which is caused by the
2+
Fig. 9 (a) Emission spectra of TCZ-004 in DMA solution upon the addition of various concentrations of Ni ; (b) Emission spectra of TCZ-004 in DMA solution upon the
3
+
2+
addition of various concentrations of Eu ; (c) The relationship of luminescence colour of TCZ-004 and Ni concentration in DMA; (d) The relationship of luminescence
3+
colour of TCZ-004 and Eu concentration in DMA.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 9
Please do not adjust margins

PleaseC dr oy sn t oE tn ag dCj uo smt mm argins
Page 10 of 12
ARTICLE
replacement of DMA molecules in TCZ-001 by H O or EtOH
Journal Name
2
Acknowledgements
View Article Online
DOI: 10.1039/C7CE00361G
The authors gratefully acknowledge financial support from the
National Natural Science Foundation of China (21233009 and
1203194), the 973 program (2014CB845603), the Strategic
Priority Research Program of the Chinese Academy of Sciences
Grant No. XDB20000000.
7
8-81
molecules.
It was also found in TCZ-003 and TCZ-004 that selective
2+
sensing of Ni ions in DMA solution (Fig. 8, 9c). Comparing
2
with the application of TCZ-001 and TCZ-004, the application
2+
，
of TCZ-003 has a better resolution in the range of Ni
concentration less than 0.20 M. But in the range from 0.20 M
to 0.35 M, TCZ-001 performs better than others in resolution.
2+
And the measurement of Ni concentration by TCZ-004 was
better than the measurement by TCZ-001 and TCZ-003 in
water or ethanol solution. (Fig. S12) Perhaps it is due to the 2D
structure of TCZ-004, which is more stable than the 1D
structure of TCZ-001 and TCZ-003 when the DMA molecules
Notes and references
1
2
3
X. Sun, Y. Wang and Y. Lei, Chem. Soc. Rev., 2015, 44, 8019.
Z. Hu, B. J. Deibert and J. Li, Chem. Soc. Rev., 2014, 43, 5815.
M. G. Campbell, S. F. Liu, T. M. Swager and M. Dincꢀ, J. Am.
Chem. Soc., 2015, 137, 13780.
replaced by H O or EtOH molecules. Thus, TCZ-001 and TCZ-
4
5
6
7
8
9
Y. Guo, X. Feng, T. Han, S. Wang, Z. Lin, Y. Dong and B. Wang,
J. Am. Chem. Soc., 2014, 136, 15485.
L.D. Tran, J. Ma, A. G. Wong-Foy and A. J. Matzger. Chem.
Eur. J., 2016, 22, 5509.
P.Q. Liao, X.W. Chen, S.Y. Liu, X.Y. Li, Y.T. Xu, M. Tang, Z. Rui,
H. Ji, J. P. Zhang and X.M. Chen, Chem. Sci., 2016, 7, 6528.
2
0
03 might be two potential luminescent probes for detection
2+
2+
of Ni in DMA. And TCZ-004 could be used to sense Ni
concentration in H O or EtOH.
2
2+
In addition to detecting Ni concentration, a remarkable
phenomenon which exhibits an obvious luminescent and
J. B. DeCoste and G. W. Peterson, Chem. Rev., 2014, 114
695.
H. Xu, X.F. Liu, C.S. Cao, B. Zhao, P. Cheng and L.N. He, Adv.
,
3+
5
colorimetric response to Eu ions in DMA was noticed in the
test process by TCZ-004 (Fig. S11). Moreover, the luminescent
Sci., 2016, 3, 1600048.
3+
and colorimetric response depends on the Eu concentration.
D. J. Tranchemontagne, J. L. Mendoza-Cortes, M. O'Keeffe
3+
Therefore, the spectrum of TCZ-004 with Eu was also
and O. M. Yaghi, Chem. Soc. Rev., 2009, 38, 1257.
transformed into the CIE 1931 coordinates (Fig. 9d). It is also 10 C Liu and B Yan. Photochem, Photobiol. Sci., 2015, 14, 1644.
2+
1
1
1
1
1
1
1 L. Lu, C. Chen, D. Zhao, J. Sun and X. Yang, Anal. Chem., 2016,
88, 1238.
found that there is a tiny replacement of Cd ions in TCZ-004
3
+
by Eu
ions (Fig. S13a). However, the measurement
2 L. Marciniak and A. Bednarkiewicz, Phys. Chem. Chem. Phys.,
3+
resolutions of Eu concentrations in H O or EtOH are too low
to be utilized to detect Eu . The difference between detecting
Ni and Eu may be tentatively assigned to the size of Eu ion
and the rate of the transmetalation reactions.
2
2
016, 18, 15584.
3+
3 J. Chen, F. Y. Yi, H. Yu, X. Liu, L. Han and G. Pang, Eur. J. Inorg.
Chem., 2016, 3994.
2+
3+
3+
4 L. Z. Yang, J. Wang, A. M. Kirillov, W. Dou, C. Xu, R. Fang, C.L.
Xu and W. S. Liu, CrystEngComm, 2016, 18, 6425.
5 P. Silva, S. M. F. Vilela, J. P. C. Tome and F.A. Almeida Paz,
Chem. Soc. Rev., 2015, 44, 6774.
6 A. Douvali, A. C. Tsipis, S. V. Eliseeva, S. Petoud, G. S.
Papaefstathiou, C. D. Malliakas, I. Papadas, G. S. Armatas, I.
Margiolaki, M. G. Kanatzidis, T. Lazarides and M. J Manos,
Angew. Chem. Int. Ed., 2015, 54, 1651.
All in all, TCZ-004 has the potential application as a
multiresponsive probe for the detection of the concentration
2+
3+
of Ni or Eu under certain condition.
Conclusions
1
7 N. Du, J. Song, S. Li, Y. X. Chi, F. Y. Bai and Y. H. Xing, ACS Appl.
Mater. Interfaces, 2016, , 28718.
In summary, five newly porous luminescent coordination
polymers based on a novel rigid carboxylate ligand (2,7-bis(4- 18 W. Liu, X. Huang, C. Xu, C. Chen, L. Yang, W. Dou, W. Chen, H.
benzoic acid)-N-(4-benzoic acid) carbazole) have been self-
assembled in hydrothermal reaction. TCZ-001 and TCZ-003 are
8
Yang and W. Liu, Chem. Eur. J., 2016, 22, 18769.
1
2
9 Y. Cui, B. Chen and G. Qian, Coordin. Chem. Rev., 2014, 273–
2
74, 76.
1
D infinite linear chain, which show potential as probe
0 M. Gharehbaghi, F. Shemirani and M.D. Farahani, J. Hazard.
Mater., 2009, 165, 1049.
2+
materials in selectively and sensitively detecting Ni
concentration in DMA, H O or EtOH solution. Exchanging 21 M. Rozga, M. Koniecki, M. Dadlez and W. Bal, Chem. Res.
2
2+
2+
Toxicol., 2010, 23, 336.
partial Zn cations by Ni cations during the pre-treatment
can change the colour of the emitting light. The process of
2
2
2 J. N. Hao and B. Yan, J. Mater. Chem. A, 2014, 2, 18018.
3 G. Xie, Y. Shi, F. Hou, H. Liu, L. Huang, P. Xi, F. Chen and Z.
Zeng, Eur. J. Inorg. Chem. 2012, 327.
2+
detecting Ni will not be disturbed by the intensity of the
excitation light source or the slit width of the fluorescence 24 D. M. Templeton and Y. Liu, Chem. Biol. Interact., 2010, 188
spectrometer. TCZ-002 is a 3D framework with a 1D channel.
,
267.
2
2
5 P. Wu, Y. Liu, Y. Liu, J. Wang, Y. Li, W. Liu and J. Wang, Inorg.
Chem., 2015, 54, 11046.
TCZ-004 is a 2D layered network and can be used in detecting
2+
3+
the concentration of Ni in DMA, H O or EtOH and Eu in
2
6 T. W. Duan, B. Yan and H. Weng, MICROPOR. MESOPOR.
MAT. 2015, 217, 196.
DMA solution. TCZ-005 is a complicated 1D structure which
belongs to Pn space group. These CPs possibly be utilized as 27 S. Dang, E. Ma, Z. M. Sun and H. Zhang, J. Mater. Chem.,
novel porous luminescent material to detecting other diverse
metal ion or small molecules. And the applications of these CPs
are under investigation in our group.
2012, 22, 16920.
8 F. Y. Yi, D. Chen, M. K. Wu, L. Han and H. L. Jiang,
ChemPlusChem, 2016, 81, 675.
9 J. Jia, J. N. Xu, S. Y. Wang, P. C. Wang, L. J. Gao, J. Chai, L. L.
Shen, X. B. Chen, Y. Fan and L. Wang, CrystEngComm, 2016,
18, 7126.
2
2
1
0 | J. Name., 2012, 00, 1-3
This journal is © The Royal Society of Chemistry 20xx
Please do not adjust margins

Page 11 of 12
PleaseC dr oy sn t oE tn ag dCj uo smt mm argins
Journal Name
ARTICLE
3
3
0 H. M. Hamid, J. Braz. Chem. Soc., 2011, 22, 1056.
62 Z. Su, J. Fan, T. A. Okamura, M. S. Chen, S. S. Chen, W. Y.
View Article Online
1 L Li, Q Chen, Z Niu, X Zhou, T Yang and W Huang, J. Mater.
Sun and N. Ueyama, Cryst. Growth Des., 2010, 10, 1911.
DOI: 10.1039/C7CE00361G
Chem. C., 2016,
4
, 1900.
63 X. L. Wang, Y. F. Bi, G. C. Liu, H. Y. Lin, T. L. Hu and X. H.
3
3
2 L. Li, C. X. Li, Y. L. Ren, M. Song, Y. Ma and R. D. Huang,
CrystEngComm, 2016, 18, 7787.
Bu, CrystEngComm, 2008, 10, 349.
64 P. Deria, D. A. Gomez-Gualdron, W. Bury, H. T. Schaef, T. C.
Wang, P. K. Thallapally, A. A. Sarjeant, R. Q. Snurr, J. T. Hupp
and O. K. Farha, J. Am. Chem. Soc., 2015, 137, 13183.
65 U. Sheridan, J. F. Gallagher, A. Philippidis and J. McGinley,
Inorg. Chim. Acta, 2015, 421, 50.
3 I. T. Choi, M. J. Ju, S. H. Kang, M. S. Kang, B. S. You, J. Y. Hong,
Y. K. Eom, S. H. Song and H. K. Kim, J. Mater. Chem. A., 2013,
1
, 9114.
3
3
3
3
4 A. D. Finke, D. E. Gross, A. Han, Moore and J. S. Moore, J. Am.
Chem. Soc., 2011, 133, 14063.
66 P. Deria, D. A. Gomez-Gualdron, I. Hod, R. Q. Snurr, J. T.
Hupp and O. K. Farha, J. Am. Chem. Soc., 2016, 138, 14449.
67 P. Deria, J. Yu, R. P. Balaraman, J. Mashni and S. N. White,
Chem. Commun., 2016, 52, 13031.
68 H. Zhang, C. Lin, T. Sheng, S. Hu, C. Zhuo, R. Fu, Y. Wen, H. Li,
S. Su and X. Wu, Chem. Eur. J., 2016, 22, 4460.
5 K. R. J. Thomas, J. T. Lin, Y.T. Tao and C.W. Ko, J. Am. Chem.
Soc., 2001, 123, 9404.
6 N. Xie, J. Wang, Z. Guo, G. Chen and Q. Li. Macromol, Chem.
Phys., 2013, 214, 1710.
7 H. J. Cheng, H. X. Tang, Y. L. Shen, N. N. Xia, W. Y. Yin, W. Zhu,
X. Y. Tang, Y. S. Ma and R. X. Yuan, J. Solid. State. Chem., 69 S. Wang, L. Shan, Y. Fan, J. Jia, J. Xu and L. Wang, J. Solid.
2
015, 232, 200.
8 M. Eddaoudi, Ł. Weseliński and R. Luebke, Synthesis, 2014, 70 A. C. Harris and I. L. Weatherall, Journal of the Royal Society
, 596. of N. Z., 1990, 20, 253.
9 X. Liu, Y. Sun, Y. Zhang, F. Miao, G. Wang, H. Zhao, X. Yu, H. 71 T. Smith and J. Guild, Trans. Opt. Soc., 1932, 33, 73.
Liu and W. Y. Wong, Org. Biomol. Chem., 2011, , 3615. 72 M. Lalonde, W. Bury, O. Karagiaridi, Z. Brown, J. T. Hupp and
O. K. Farha, J. Mater. Chem. A, 2013, , 5453.
State. Chem., 2017, 245, 132.
3
3
4
4
4
4
4
4
4
6
9
0 B. Hu, X. Lv, J. Sun, G. Bian, M. Ouyang, Z. Fu, P. Wang and C.
Zhang, Org. Electron., 2013, 14, 1521.
1
73 Y.J. Hu, J. Yang, Y. Y. Liu, S. Song and J. F. Ma, Cryst. Growth
Des. 2015, 15, 3822.
1 L. Li, S. Tang, X. Lv, M. Jiang, C. Wang and X. Zhao, New J.
Chem., 2013, 37, 3662.
74 L. L. Lv, J. Yang, H. M. Zhang, Y. Y. Liu and J. F. Ma, Inorg.
Chem. 2015, 54, 1744.
2 A. B. Kumar, J. M. Anderson and R. Manetsch, Org. Biomol.
Chem., 2011,
9
, 6284.
75 J. Li, L. Li, H. Hou and Y. Fan, Cryst. Growth Des., 2009, 9,
3 P. P. Bag, D. Wang, Z. Chen and R. Cao, Chem. Commun.,
4504.
2
016, 52, 3669.
76 F. Li, J. J. Hu, L. L. Koh and T. S. Hor, Dalton Trans., 2010,
4 H. J. Cheng, X. Y. Tang, R. X. Yuan and J. P. Lang,
39, 5231.
CrystEngComm, 2016, 18, 4851.
J. Jia, X. Lin, C. Wilson, A. J. Blake, N. R. Champness, P.
77 K. Suman, F. Baig, R. kant, V. K. Gupta, S. Mandal and M.
Sarkar, RSC Adv., 2014, 4, 36451.
5
Hubberstey, G. Walker, E. J. Cussen and M. Schroder, Chem. 78 A. Pal, S. Chand, S. Senthilkumar, S. Neogi and M. C. Das,
Commun., 2007, 840
.
CrystEngComm, 2016, 18, 4323.
4
4
4
6 Y. Ooyama, N. Yamaguchi, I. Imae, K. Komaguchi, J. Ohshita 79 L. Granato, S. Laurent, L. Vander Elst, K. Djanashvili, J. A.
and Y. Harima, Chem. Commun., 2013, 49, 2548.
Peters and R. N. Muller, Contrast Media Mol. Imaging,
7 J. R. Li, A. A. Yakovenko, W. Lu, D. J. Timmons, W. Zhuang, D.
Yuan and H. C. Zhou, J. Am. Chem. Soc., 2010, 132, 17599.
8 G. M. Shedrick, SHELXL-97, program for Refining Crystal
2011, 6, 482.
80 G. M. Pawar, J. B. Sheridan and F. Jäkle, Eur. J. Inorg. Chem.
2016, 2227.
Structure Refinement, University of Göttingen, Germany, 81 M. Taddei, A. Ienco, F. Costantino and A. Guerri, RSC Adv.,
1
997.
9 A. L. Spek, PLATON, Amultipurpose crystallographic tool; 82 K. Akhbari, K. Alizadeh, A. Morsali and M. Zeller, Inorg.
Utrecht University: Utrecht, The Netherlands, 2001. Chim. Acta, 2009, 362, 2589.
0 Y. Wang, C. Tan, Z. Sun, Z. Xue, Q. Zhu, C. Shen, Y. Wen, S. Hu, 83 Y. Han, H. Xu, Y. Liu, H. Li, H. Hou, Y. Fan and S. R. Batten,
Y. Wang, T. Sheng and X. Wu, Chem. Eur. J., 2014, 20, 1341. Chem. Eur. J., 2012, 18, 13954.
X. T. Zhang, L. M. Fan, W. L. Fan, B. Li, G. Z. Liu, X. Z. Liu 84 Z. Lei, X. L. Pei, Z. G. Jiang and Q. M. Wang, Angew. Chem.
and X. Zhao, CrystEngComm, 2016, 18, 6914. Int. Ed., 2014, 53, 12771.
X. Y. Wan, F. L. Jiang, L. Chen, J. Pan, K. Zhou, K. Z. Su, J.D. 85 Z. Z. Lu, R. Zhang, Z. R. Pan, Y. Z. Li, Z. J. Guo and H. G.
Pang, G. X. Lyu and M. C. Hong, CrystEngComm, 2015, 17 Zheng, Chem. Eur. J., 2012, 18, 2812.
829.
2013, 3, 26177.
4
5
5
5
1
2
,
3
5
5
5
3
4
5
S. Yuan, Y. K. Deng, W. M. Xuan, X. P. Wang, S. N. Wang,
J. M. Dou and D. Sun, CrystEngComm, 2014, 16, 3829.
Y. Gai, F. Jiang, L. Chen, M. Wu, K. Su, J. Pan, X. Wan and
M. Hong, Cryst. Growth Des., 2014, 14, 1010.
L. Zhang, Y. Zhang, R. Wang, Z. Kang, X. Liu, D. Sun and
Q. Meng, CrystEngComm,2015, 17, 6591.
5
5
6
7
T. Liu, S. Wang and J. Bai, CrystEngComm, 2013, 15, 5476.
X. Liu, Z. Xiao, A. Huang, W. Wang, L. Zhang, R. Wang
and D. Sun, New J. Chem., 2016, 40, 5957.
5
5
8
9
J. M. Hao, B. Y. Yu, K. Van Hecke and G. H. Cui,
CrystEngComm, 2015, 17, 2279.
Yong-Liang Shao, Yan-Hui Cui, Jin-Zhong Gu, Alexander
M. Kirillov, Jiang Wu and Y. W. Wang, RSC Adv., 2015, 5,
8
7484.
6
6
0
1
M. D. Zhang, L. Qin, H. T. Yang, Y. Z. Li, Z. J. Guo and H.
G. Zheng, Cryst. Growth Des., 2013, 13, 1961.
H. Y. Liu, H. Wu, J. F. Ma, Y. Y. Liu, B. Liu and J. Yang,
Cryst. Growth Des., 2010, 10, 4795.
This journal is © The Royal Society of Chemistry 20xx
J. Name., 2013, 00, 1-3 | 11
Please do not adjust margins

CrystEngComm
Page 12 of 12
View Article Online
DOI: 10.1039/C7CE00361G
Graphical Abstract
2+
Five coordination polymers, based on a novel carbazole-based ligand, show a linear correlation to Ni and
3
+
Eu concentration.