1

Supporting Information

Rational route to SCM materials based on 1-D cobalt selenocyanato

coordination polymer

Jan Boeckmann and Christian Näther*

Figure Content Page

S1 Thermal ellipsoid plot for 1. 2

Tab.1 Selected bond lengths [Å] and angles [°] for 2. 2

S2 DTG, TG, DTA and MS trend scan curves for 1. 3

S3 Heating rate dependent TG measurements for 1. 3

S4 Experimental XRPD patterns of the intermediates isolated in several TG

runs.

4

S5 Isothermal XRPD measurements at 100°C of [Co(NCSe)2(pyridine)4] (1). 4

S6 IR and Raman spectra for compound 1. 5

S7 IR and Raman spectra for compound 2. 5

S8 DC susceptibility measurements for [Co(NCSe)2(pyridine)4] (1). 6 S9 Magnetization saturation experiments for [Co(NCSe)2(pyridine)2]n (2) 6

S10 Zero-field-cooled (ZFC) and field-cooled (FC) magnetic measurements for 2. 7

S11 Isothermal frequency dependence of χM' and χM'' at 4.5 K for compound 2. 7

S12 Plot of ln(χM*T) vs. T-1 for 2. 8

S13 Experimental and calculated XRPD pattern for 1. 8

S14 Difference plot of the Rietveld refinement of [Co(NCSe)2(pyridine)2]n (2). 9

S15 Experimental and calculated XRPD pattern for 2. 9 - Further experimental details 10 ff

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Figure S1. Thermal ellipsoid plot of the crystal structure of [Co(NCSe)2(pyridine)4] (1) with

view of the coordination sphere of the metal cation with labeling and displacement ellipsoids

drawn at the 30% probability level. Symmetry codes: A = -x + 3/2, -y + 3/2, -z + 1.

Table 1. Selected bond lengths [Å] and angles [°] for 2.

[Co(NCSe)2(pyridine)2]n (2)Co(1)-N(1A) 2.045(3) Co(2)-N(31) 2.205(2) Co(1)-N(2) 2.346(3) Co(2)-Se(2) 2.5350(4) Co(1)-N(11) 2.230(3) N(1)-C(1)-Se(1) 176.2(2) Co(1)-N(21) 2.266(3) N(2)-C(2)-Se(2) 178.8(2) Co(1)-Se(3) 2.7921(5) N(3)-C(3)-Se(3) 178.8(3) Co(1)-Se(1) 2.921(3) N(11)-Co(1)-N(21) 174.63(11)Co(2)-N(3) 2.193(3) N(31)-Co(2)-N(31A) 180.0

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50 100 150 200 250 300 350 400

m/z = 79

MID

(d

m/d

T),

Δm

, ΔT

and

ion

curr

ent

/ ar

b. u

nits

endo

Δm = 27.31 %

DTG

TGT

P = 164 °C

TP = 131 °C

m/z = 52

MID

DTA

Temperature / °C

Figure S2. DTG, TG, DTA and MS trend scan curves of [Co(NCSe)2(pyridine)4] (1). Heating

rate = 4 °C/min; given are the peak temperatures TP (°C) and mass changes (%).

50 100 150 200 250 300 350

R

elat

ive

inte

nsity

/ a

rb.

units

Temperature / °C

Heating Rate

1 / 4 / 8 °C min-1

1:2 compound formed

Figure S3. Heating rate dependent TG measurements for [Co(NCSe)2(pyridine)4] (1).

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10 20 30 40 50

(C)

R

elat

ive

inte

nsity

/ a

rb.

units

(A)

(B)

2 Theta / °

Figure S4. Experimental XRPD patterns of the intermediates isolated in several TG runs at

about 160°C (A and B) together with calculated XRPD pattern (C) of [Co(NCSe)2(pyridine)4]

(1).

Figure S5. Isothermal XRPD measurements at 100°C of [Co(NCSe)2(pyridine)4] (1).

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2500 2000 1500 1000 500

In

tens

ity /

arb

. un

its

2070 cm-1

2072 cm-1

Wavenumber cm-1

Figure S6. IR (top) and Raman (bottom) spectra for compound [Co(NCSe)2(pyridine)4] (1).

Expected for terminal bonded NCSe anions ~ 2050 cm-1.1

2500 2000 1500 1000 500

In

tens

ity /

arb

. un

its

2106 cm-1

2097 cm-1

Wavenumber cm-1

2105 cm-1

Figure S7. IR (top) and Raman (bottom) spectra for compound [Co(NCSe)2(pyridine)2]n (2).

Expected for µ-1,3 bridging NCSe anions ≥ 2100 cm-1.1

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0 50 100 150 200 250 3000

1

2

3

4

5 χM (para)*T

/ K cm

³ mol -1

1,5

2,0

2,5

3,0

3,5

χ M(p

ara)

/ c

m³

mol

-1 (

*10-1

)

Temperature / K

Figure S8. DC susceptibility measurements for [Co(NCSe)2(pyridine)4] (1). The decrease of

the χM*T vs. T values are typical for CoII cations and can be traced back to spin orbit coupling

and zero field splitting.

-5 -4 -3 -2 -1 0 1 2 3 4 5

-2

-1

0

1

2

M /

Nβ

mol

-1

Applied field / T (*10-1)

BR = 0.06 Nβ mol-1

HC = 0.0008 T

0,0 0,2 0,4 0,6 0,8

Figure S9. Magnetization saturation experiments for [Co(NCSe)2(pyridine)2]n (2). Hysteresis

loop in the range of ± 0.5 T and 4.5 K.

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5 10 15 20 25

0

10

20

30

40

50

ZFC FC

χ M /

cm

³ m

ol-1

Temperature / K

Figure S10. Zero-field-cooled (ZFC) and field-cooled (FC) magnetic suscetibility

measurements at HDC = 0.01 T.

0 2000 4000 6000 8000 10000

5

10

15

20

25

Frequency / Hz

1

2

3

4

5

6

7

χ M

' / c

m³

mol

-1χ

M

'' / cm³ m

ol -1

Figure S11. Isothermal frequency dependence of χM' and χM'' at 4.5 K for compound 2.

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0,0 0,1 0,2 0,3 0,4 0,51,0

1,5

2,0

2,5

3,0

3,5

4,0

ln(χ

M*T

)

T -1/ K-1

Δξ = 4JS2

S = 1/2 J = 20.7 K = 2.9 * 10-22 J

S = 3/2 J = 2.3 K = 3.2 * 10-23 J

Figure S12. Plot of ln(χM*T) vs. T-1 for 2.

5 10 15 20 25 30 35 40 45 50 55

Rel

ativ

e in

tens

ity /

arb

. un

its

(A)

(B)

2 Theta / °

Figure S13. Experimental (A) and calculated (B) XRPD pattern for compound

[Co(NCSe)2(pyridine)4] (1).

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Figure S14. Difference plot of the Rietveld refinement of [Co(NCSe)2(pyridine)4] (1).

10 15 20 25 30 35 40 45

Rel

ativ

e in

tens

ity /

arb

. un

its

(A)

(B)

2 Theta / °

Figure S15. Experimental (A) and calculated (B) XRPD pattern for compound

[Co(NCSe)2(pyridine)2]n (2).

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Further experimental details

Rietveld Refinement. The Rietveld refinement was performed using Fullprof2k with the

Winplotr software package.2, 3 The cell parameters were refined with WinXPOW Software

package.4 After the initial refinements of the scale factors, unit cell parameters, and profile

parameters, the organic part was refined using soft constrains for the pyridine and

selenocyanato ligands. All atoms were refined isotropically and the H atoms were not

considered.

Single-Crystal Structure Analysis. The investigation was performed with an imaging plate

diffraction system (IPDS-2) with Mo-Kα-radiation from STOE & CIE. The structure solution

was done with direct methods using SHELXS-975 and structure refinements were performed

against |F|2 using SHELXL-97.5 A numerical absorption correction was applied using X-Red

Version 1.31 and X-Shape Version 2.11 of the Program Package X-Area.6 All non-hydrogen

atoms were refined with anisotropic displacement parameters. All hydrogen atoms were

positioned with idealized geometry and were refined with fixed isotropic displacement

parameters [Ueq(H) = -1.2·Ueq(C)] using a riding model with dC-H = 0.93 Å.

X-ray Powder Diffraction (XRPD). XRPD experiments were performed using 1) a Stoe

Transmission Powder Diffraction System (STADI P) with Cu-Kα-radiation (λ = 154.0598 pm)

that is equipped with a linear position-sensitive detector (Delta 2 Theta = 6.5-7° simultaneous;

scan range overall = 2-130°) from STOE & CIE and an Image Plate Detector (scan range

overall = 0-127°) and 2) a PANalytical X‘Pert Pro MPD Reflection Powder Diffraction

System with Cu-Kα radiation (λ = 154.0598 pm) equipped with a PIXcel semiconductor

detector from PANalytical.

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Differential Thermal Analysis, Thermogravimetry, and Mass Spectroscopy (DTA-TG-

MS). The DTA-TG measurements were performed in a nitrogen atmosphere (purity: 5.0) in

Al2O3 crucibles using a STA-409CD instrument from Netzsch. The DTA-TG-MS

measurements were performed with the same instrument, which is connected to a quadrupole

mass spectrometer from Balzers via Skimmer coupling from Netzsch. The MS measurements

were performed in analogue and trend scan mode in Al2O3 crucibles in a dynamic nitrogen

atmosphere (purity: 5.0) using heating rates of 4 °C/min. All measurements were performed

with a flow rate of 75 mL/min. The instrument was calibrated using standard reference

materials.

Spectroscopy. Fourier transform IR spectra were recorded on a Genesis series FTIR

spectrometer, by ATI Mattson, in KBr pellets.

Magnetic measurements. Magnetic measurements were performed using a Physical Property

Measuring System (PPMS) from Quantum Design, which is equipped with a 9 T magnet. The

data were corrected for core diamagnetism.7

References

1. This reference refers to thiocyanato analogues, whose IR spectroscopic data should be similar with selenocyanates:R. A. Bailey, S. L. Kozak, T. W. Michelsen and W. N. Mills, Coord. Chem. Rev, 1971, 6, 407-445.

2. T. Roisnel and J. Rodriguez-Carvajal, Proceedings of the Seventh European Powder Diffraction Conference (EPDIC 7), 2000.

3. J. Rodriguez-Carvajal, Physica B-Condensed Matter, 1993, 192, 55. 4. WinXPOW, Version 2.23, STOE & CIE GmbH, Darmstadt, Germany, 2003. 5. G. M. Sheldrick, Acta Cryst., 2008, A64, 112-122. 6. X-Area, Version 1.44, Program Package for Single Crystal Measurements, STOE & CIE

GmbH, Darmstadt, Germany, 2008. 7. G. A. Bain and J. F. Berry, J. Chem. Educ., 2008, 85, 532-536.

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