Structural diversity of zinc(II) coordination polymers with … · 2019. 2. 22. · 1 Electronic...

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1 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. Fedin 1,2 1 Nikolaev Institute of Inorganic Chemistry SB RAS, 3 Akad. Lavrentiev Av., 630090, Novosibirsk, Russian Federation. 2 Novosibirsk State University, 2 Pirogova Street, 630090 Novosibirsk, Russian Federation 3 N.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

Transcript of Structural diversity of zinc(II) coordination polymers with … · 2019. 2. 22. · 1 Electronic...

Page 1: Structural diversity of zinc(II) coordination polymers with … · 2019. 2. 22. · 1 Electronic Supplementary Information (ESI) for Structural diversity of zinc(II) coordination

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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

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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

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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