Structural diversity of zinc(II) coordination polymers with … · 2019. 2. 22. · 1 Electronic...
Transcript of Structural diversity of zinc(II) coordination polymers with … · 2019. 2. 22. · 1 Electronic...
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Electronic Supplementary Information (ESI) for
Structural diversity of zinc(II) coordination polymers with
octafluorobiphenyl-4,4’-dicarboxylate based on
mononuclear, paddle wheel and cuboidal units
Anastasia M. Cheplakova,1,2 Konstantin A. Kovalenko,1,2 Denis G. Samsonenko,1,2 Andrey S.
Vinogradov,3 Victor M. Karpov,3 Vyacheslav E. Platonov,3 Vladimir P. Fedin1,2
1Nikolaev Institute of Inorganic Chemistry SB RAS, 3 Akad. Lavrentiev Av., 630090, Novosibirsk, Russian
Federation.
2Novosibirsk State University, 2 Pirogova Street, 630090 Novosibirsk, Russian Federation
3N.N. Vorozhtsov Novosibirsk Institute of Organic Chemistry SB RAS, 9 Acad. Lavrentiev Av., 630090,
Novosibirsk, Russian Federation
Identification codes
(1) – [Zn(eg)3](oFBPDC)
(2) – [Zn(H2O)(ur)(oFBPDC)]
(3) – [Zn(CH3OH)(CH3OCH2CH2OH)(oFBPDC)]
(4) – [Zn2(CH3CN)2(oFBPDC)2]·2C6H6·2CH3CN
(5) – [Zn2(H2O)2(oFBPDC)2]·4(CH3)2CO
(6) – [{Zn4(µ3-OCH3)4}(CH3OH)4(oFBPDC)2]∙[{Zn4(µ3-OCH3)4}(H2O)(CH3OH)3(oFBPDC)2]∙13CH3OH
H2oFBPDC – octafluorobiphenyl-4,4’-dicarboxylic acid
eg – ethylene glycol
ur – urotropine, hexamethylenetetramine
Corresponding author
E-mail: [email protected], [email protected]; Fax: +7 (383) 330 9489; Tel: +7 (383) 330 9490
Electronic Supplementary Material (ESI) for CrystEngComm.This journal is © The Royal Society of Chemistry 2019
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Ligand synthesis
Scheme S1. The synthesis of H2oFBPDC.
19F and 1H NMR spectra were recorded on a Bruker AV 300 instrument (282.4 and 300 MHz) using
(CD3)2CO + CCl4 as a solvent. The chemical shifts of the 1H and 19F NMR spectra were referenced to
internal solvent resonances (2.05 from TMS) and C6F6 (–162.9 ppm from CCl3F).
Fig. S1. 1H NMR spectrum of H2oFBPDC.
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Fig. S2. 19F NMR spectrum of H2oFBPDC.
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Crystal structures and FT-IR spectrum of complexes 1-6
Fig. S3. The FT-IR spectrum of 1.
Fig. S4. Packing of the chains in 2. View along the b axis. Hydrogen atoms are omitted for clarity.
4000 3500 3000 2500 2000 1500 1000 500
0
10
20
30
40
50
60
70
sCOO)
aCOO)
C-F)
C-H)
O-H)
tra
nsm
itta
nce
, %
wavenumber, cm-1
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Fig. S5. Coordination environment of Zn(II) cations in the structure 3 (50% probability ellipsoids). Hydrogen
atoms are omitted for clarity. The alternative orientation of disordered 2-methoxyethanol and methanol are
shown with dashed lines.
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Fig. S6. The single crystals of 4 of a few millimeters in size.
Fig. S7. Packing of the layers in 4. View along the b axis. Guest molecules of benzene and acetonitrile and hydrogen
atoms are omitted for clarity.
1 mm
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Fig. S8. The FT-IR spectrum of complex 4.
4000 3500 3000 2500 2000 1500 1000 500
10
20
30
40
50
60
70
80
90
C-F)
sCOO)
aCOO)
CN)
tra
nsm
itta
nce
, %
wavenumber, cm-1
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Fig. S9. Coordination environment of Zn(II) cations in the structure 5. Hydrogen atoms are omitted for
clarity. Hydrogen bonds are shown with dashed lines.
Fig. S10. Packing of the layers in 5. View along the a axis. Guest molecules of acetone and hydrogen atoms are
omitted for clarity.
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Fig. S11. Packing of the layers in 5. View along the c axis. Guest molecules of acetone and hydrogen atoms are
omitted for clarity.
Fig. S12. The FT-IR spectrum of complex [Zn2(H2O)2(oFBPDC)2]∙1.3(CH3)2CO.
4000 3500 3000 2500 2000 1500 1000 500
0
20
40
60
80
100
C-F)
O-H)
tra
nsm
itta
nce
, %
wavenumber, cm-1
aCOO)
sCOO)
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Fig. S13. The system of hydrogen bonds (shown with dashed lines) in structure 6.
a)
b)
Fig. S14. Representation of the free solvent accessible void volume in crystal structure 6: a) view along c axis; b)
view along a axis.
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Fig. S15. The FT-IR spectrum of complex 6.
4000 3500 3000 2500 2000 1500 1000 500
20
30
40
50
60
70
80
90
C-F)
sCOO)
aCOO)
C-H)
O-H)
tra
nsm
itta
nce
, %
wavenumber, cm-1
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Thermal analysis
Fig. S16. TG curve of complex 1.
Fig. S17. TG (solid) and DTG (dashed) curves of complexes 4 (black) and 5 (red).
[#] Instrument
[1] TG 209 F1
[2] TG 209 F1
File
4808.dt3
c-DTA_4808.dt3_0.mt3
Date
2018-08-01
2018-08-01
Identity
SN742
SN742
Sample
[Zn(eg)3](oFBPDC)
[Zn(eg)3](oFBPDC)
Mass/mg
10.300
10.300
Segment
1/1
1/1
Range
20/10.0(K/min)/400
19/10.0(K/min)/385
Atmosphere
He, 30.0ml/min / He, 30.0ml/min
He, 30.0ml/min / He, 30.0ml/min
Corr.
TG:520
5
-2.5
-2.0
-1.5
-1.0
-0.5
0.0
0.5
1.0
c-DTA /K
50 100 150 200 250 300 350Temperature /°C
40
50
60
70
80
90
100
TG /%
0
50
100
150
200
250
Flow /(ml/min)
-20
-15
-10
-5
0
DTG /(%/min)
Main 2018-08-01 12:16 User: plus
Residual Mass: 40.13 % (385.2 °C)
[1]
[1][1]
[1]
[2]
exo
40
50
60
70
80
90
100
50 100 150 200 250 300 350 400
-10
-5
0
5
10
Mass, %
DT
G, %
/min
Temperature, °C
4
5
88.7%150 °C
91.4%160 °C
85.6%
215 °C
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Adsorption properties of coordination polymers 4 and 5
Fig. S18. The comparison of FT-IR spectra of pristine and activated compounds 4 and 5 as well as
[Zn2(CH3CONH2)2(oFBPDC)2].
Fig. S19. Pore size distribution for activated 4 and 5.
(CN)ν
a(COO)ν
s(COO)ν
(C–F)ν
(C–H)ν
(C–H)ν
(O–H)ν
[Zn2L2(oFBPDC)2]
500 1000 1500 2000 2500 3000 3500 4000
tra
nsm
itta
nce
, %
wavenumber, cm−1
L = CH3CN (4)
activated 4
L = H2O (5)
activated 5
L = CH3CONH2
0
0.1
0.2
0.3
0.4
0.5
0.6
0 0.5 1 1.5 2 2.5 3 3.5 4
0
0.02
0.04
0.06
0.08
0.1
0.12
dV
(d),
mL
/nm
/g
Half pore width, nm
4, dV(d)
4, Pore Volume
5, dV(d)
5, Pore Volume
Cu
mu
lative
Po
re V
olu
me
, m
L/g