Supplementary Materials

Supplementary Materials Two-Dimensional Metal-Organic Frameworks (MOFs) Constructed from Heterotrinuclear Coordination Units and 4,4’-Biphenyldicarboxylate (BPDC) Ligands: [Zn2M(BPDC)3(DMF)2]·4DMF (M = CoII, NiII, or CdII, DMF = N,N’-Dimethyl formamide)

Yonghui Wang,a,b Björn Bredenkötter,a Bernhard Rieger,a and Dirk Volkmer*a a

Institute of Materials and Catalysis, University of Ulm, Albert-Einstein-Allee 11,

Ulm, D-89081, Germany; Tel.: +49-731-50-23921, Fax: +49-731-50-23039, E-mail: [email protected]. b

Key Laboratory of Polyoxometalate Science of Ministry of Education, Faculty of

Chemistry, Northeast Normal University, Changchun, 130024, P. R. China

* To whom correspondence should be addressed (E-mail: [email protected]).

1

Fig. S1 Complete labelling scheme of compound 1 (There are two independent Co atoms in compound 1, both of which lie on an inversion center)

2

Fig. S2 Complete labelling scheme of compound 2 (Ni(1) lies on an inversion centre. Compounds 2 and 3 are isomporphous and their structures have been refined with a common origin and identical labelling schemes.)

3

1

100

o

Step 1. 70-225 C -17.34% o Step 2. 226-400 C -9.54% o Step 3. 401-580 C -36.39% o Step 4. 580-920 C -11.61%

2

Weight%

80

60

3

40

4

20

TGA curve of compound 1 0 0

200

400

600

800

1000

o

Temperature ( C)

Fig. S3 Thermogravimetric analysis (TGA) curve of compound 1.

100

1 o

2

80

Weight%

Step 1. 37-238 C, -21.69% o Step 2. 239-389 C, -9.84% o Step 3. 390-580 C, -32.55% o Step 4. 581-890 C, -10.63%

60

3 40

4

20


100

200

300

400

500

600

700

800

o

Temperature ( C)

Fig. S4 TGA curve of compound 2.

4

900

1000 1100

100 o

1

80

Weight%

Step 1. 35-380 C -33.48% o Step 2. 381-579 C -35.06% o Step 3. 579-1045 C -8.14%

60

2 40

3

20


100

200

300

400

500

600

700

800

o

Temperature ( C)

Fig. S5 TGA curve of compound 3.

5

900

1000 1100

BPDC (BPDC:BaSO4 = 1:1) 4

5x10

4

4x10

4

4

3x10

4

-1

1x10 (cm )

2x10

Kubelka-Munk Unit

0.3

0.2

0.1

Calculated absorption spectrum

0.0 200

400 4

5x10

600 4

4x10

800 4

1000 4

3x10

(nm) 4

-1

1x10 (cm )

2x10

Reflectance (%)

120

100

80

UV-vis DRS spectrum 60

40 200

400

600

800

1000 (nm)

Fig. S6 UV-vis diffuse reflectance spectrum (DRS) (bottom) and calculated absorption spectrum (top) via the Kubelka-Munk function for the BPDC ligand (BPDC:BaSO4 = 1:1).

6

Compound 1 (1:BaSO4 = 1:1) 4

0.3

5x10

4

4x10

4

4

3x10

4

-1

1x10 (cm )

2x10

Kubelka-Munk unit


0.2

0.1

0.0 200

400 4

5x10

600 4

4x10

800 4

(nm)

1000 4

3x10

2x10

4

-1

1x10 (cm )

Reflectance (%)

90 80 70 60

UV-vis DRS spectrum

50 200

400

600

800

1000 (nm)

Fig. S7 UV-vis diffuse reflectance spectrum (DRS) (bottom) and calculated absorption spectrum (top) via the Kubelka-Munk function for Compound 1 (1:BaSO4 = 1:1).

7


Kubelka-Munk unit

0.4

5x10

4

4x10

4

-1

4

3x10

4 1x10 (cm )

2x10

0.3

0.2


0.1

0.0 200

400 4

5x10

600 4

4x10

1000 (nm)

800 4

-1

4

3x10

4 1x10 (cm )

2x10

Reflectance (%)

100

80

60

UV-vis DRS spectrum 40 200

400

600

800

1000 (nm)


8


Kubelka-Munk unit

0.08

5x10

4

4x10

4

4

3x10

4

-1

1x10 (cm )

2x10

0.06

0.04


0.02

0.00 200

400 4

5x10

600 4

4x10

1000 (nm)

800 4

4

3x10

2x10

4

1x10 (cm-1)

Reflectance (%)

110 100 90 80

UV-vis DRS spectrum 70 60 200

400

600

800

1000 (nm)


9

XRPD patterns of Compound 1 at elevated temperatures

2000

o

450 C

Intensity (cps)

350 300

1500

250 200 1000

150 100 50

500

r.t. 10

20

30

40

50

o

2θ ( )

Fig. S10 X-ray Powder diffraction (XRPD) patterns of Compound 1 measured at elevated temperatures.

10

Table T1 Weak hydrogen-bonding parameters (Å and °) involving the occluded DMF molecules for 1-3 ============================================================================================ Analysis of Potential Hydrogen Bonds and Schemes with d(D...A) < R(D)+R(A)+0.50, d(H...A) < R(H)+R(A)-0.12 Ang., D-H...A > 100.0 Deg ============================================================================================ Note: - ARU codes in [] are with reference to the Coordinates printed above (Possibly transformed, when MOVE .NE. 1.555) ============================================================================================

Compound 1 ============================================================================================ Nr Typ Res Donor --- H....Acceptor [ ARU ] D - H H...A D...A D - H...A -------------------------------------------------------------------------------------------1 1 C(18) --H(18) ..O(17) 2 1 C(20) --H(20) ..O(17) 3 1 C(23) --H(23B) ..O(16) 4 Intra 1 C(24) --H(24C) ..O(7) 5 2 C(37) --H(37) ..O(16) 6 2 C(44) --H(44) ..O(18) 7 2 C(48) --H(48A) ..O(15) 8 Intra 3 C(50) --H(50A) ..O(15) 9 5 C(55) --H(55) ..O(10) 10 6 C(59) --H(59A) ..O(15)

[ [ [ [ [ [ [ [ [ [

2555.05] 4464.05] 3665.04] ] 2655.04] 2565.06] 2555.03] ] ] ]

0.94 0.94 0.97 0.97 0.94 0.94 0.97 0.97 0.94 0.97

2.50 2.34 2.56 2.35 2.57 2.47 2.37 2.27 2.55 2.28

3.432(16) 3.270(15) 3.41(2) 2.761(12) 3.492(19) 3.40(2) 3.29(3) 2.74(4) 3.356(15) 3.21(6)

173 169 147 104 166 168 158 108 143 163

:: No Classic Hydrogen Bonds Found Translation of ARU-code to Equivalent Position Code =================================================== [ 2555. ] = 1/2-x,1/2+y,1/2-z [ 4464. ] = -1/2+x,3/2-y,-1/2+z [ 3665. ] = 1-x,1-y,-z [ 2565. ] = 1/2-x,3/2+y,1/2-z [ 2655. ] = 3/2-x,1/2+y,1/2-z

Compound 2 ============================================================================================ Nr Typ Res Donor --- H....Acceptor [ ARU ] D - H H...A D...A D - H...A -------------------------------------------------------------------------------------------1 1 C(18) 2 1 C(20) 3 Intra 1 C(22) 4 Intra 2 C(27) 5 Intra 3 C(30)

--H(18) --H(20) --H(22) --H(27B) --H(30C)

..O(8) ..O(8) ..O(3) ..O(8) ..O(9)

[ [ [ [ [

4565.02] 2555.02] 4455.01] ] ]

0.95 0.95 0.95 0.98 0.98

2.57 2.46 2.58 1.92 2.07

3.47(3) 3.34(3) 3.094(14) 2.49(7) 2.51(5)

158 154 114 114 105

:: No Classic Hydrogen Bonds Found Translation of ARU-code to Equivalent Position Code =================================================== [ 4455. ] = -1/2+x,1/2-y,1/2+z [ 2555. ] = 1/2-x,1/2+y,1/2-z [ 4565. ] = 1/2+x,3/2-y,1/2+z

Compound 3 ============================================================================================ Nr Typ Res Donor --- H....Acceptor [ ARU ] D - H H...A D...A D - H...A -------------------------------------------------------------------------------------------1 1 C(13) --H(13) 2 1 C(20) --H(20) 3 Intra 1 C(22) --H(22)

..O(9) ..O(8) ..O(3)

[ [ [

1655.03] 2555.02] 4455.01]

0.95 0.95 0.95

2.33 2.43 2.59

3.215(15) 3.313(19) 3.074(7)

155 155 112

4 Intra 2 C(27) --H(27B) ..O(8) 5 Intra 3 C(30) --H(30C) ..O(9)

[ [

] ]

0.98 0.98

1.85 2.19

2.41(5) 2.64(2)

113 106

:: No Classic Hydrogen Bonds Found

Translation of ARU-code to Equivalent Position Code =================================================== [ 4455. ] = -1/2+x,1/2-y,1/2+z [ 1655. ] = 1+x,y,z [ 2555. ] = 1/2-x,1/2+y,1/2-z

For C--H...Acceptor Interactions See: Th. Steiner, Cryst. Rev, (1996), 6, 1-57 H-Bond classification: G.A.Jeffrey, H.Maluszynska & J.Mitra., Int.J.Biol.Macromol.(1985),7,336-348 also: G.A.Jeffrey & W.Saenger, Hydrogen Bonding in Biological Structures Springer-Verlag, Berlin, 1991, pp 20. ----------------------------------------------------------------------------------------------2-Centre (linear) D-H...X most prob. angle 160 deg 3-Centre (bifurcated) SUM of 3 angl. about H = 360 deg 4-Centre (trifurcated)