Eur. J. Inorg. Chem. 2008 · © WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2008 · ISSN 1434–1948

SUPPORTING INFORMATION

Title: Chemical Modification of a Bridging Ligand Inside a Metal–Organic Framework while Maintaining the 3D Structure Author(s): José Sánchez Costa, Patrick Gamez,* Cory A. Black, Olivier Roubeau, Simon J. Teat, Jan Reedijk Ref. No.: I200800002

Table S1. Crystal data and structure refinement for MOF-LIC-1.

Identification code MOF-LIC-1

Empirical formula C36H40Gd2N7O16

Formula weight 1141.25

Temperature 150(2) K

Wavelength 0.84570 Å

Crystal system Triclinic

Space group P−1 (No. 2)

Unit cell dimensions a = 10.4883(11) Å α = 100.986(2)°

b = 11.2214(12) Å β = 110.352(2)°

c = 12.7410(13) Å γ = 99.772(2)°

Volume 1334.0(2) Å3

Z 1

Density (calculated) 1.421 Mg/m3

Absorption coefficient 4.653 mm−1

F(000) 561

Crystal size 0.06 × 0.07 × 0.09 mm3

Theta range for data collection 3.8 to 31.9°

Index ranges −13<=h<=13, −13<=k<=14, −15<=l<=15

Reflections collected 9481 [R(int) = 0.0462]

Refinement method Full-matrix least-squares on F2

Data / parameters 4795 / 290

Goodness-of-fit on F2 1.09

R1 (wR2) [Fo>4σ(Fo)] R1 = 0.0401, wR2 = 0.1163

Largest diff. peak and hole 1.58 and −1.78 e.Å-3

Figure S1. Representation of the dinuclear gadolinium(III) complex unit where each metal ion is

coordinated to five different N-BDC ligands and two DMF solvent molecules (one of them is

disordered). Selected bond distances and angles are listed in Tables S2 and S4, respectively.

Figure S2. Experimental (─) and theoretical (─) X-ray powder diffraction patterns for MOF-LIC-1.

Table S2. Selected bond lengths [Å] for MOF-LIC-1.

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Gd(1)−O(1) 2.466(4) Gd(1)−O(2) 2.460(5)

Gd(1)−O(3) 2.376(3) Gd(1)−O(4d) 2.386(3)

Gd(1)−O(5) 2.410(4) Gd(1)−O(6) 2.336(4)

Gd(1)−O(6d) 2.784(4) Gd(1)−O(7) 2.442(4)

Gd(1)−O(8) 2.769(6) Gd(1)−Gd(1d) 4.073(1)

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Symmetry transformation used to generate equivalent atoms: d: −1-x,−1−y,1−z

Table S3. Selected angles [°] for MOF-LIC-1.

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O(1)−Gd(1)−O(2) 52.45(15) O(1)−Gd(1)−O(3) 73.46(13)

O(1)−Gd(1)−O(5) 81.08(14) O(1)−Gd(1)−O(6) 134.22(13)

O(1)−Gd(1)−O(7) 74.00(14) O(1)−Gd(1)−O(8) 98.88(17)

O(1)−Gd(1)−O(4d) 147.80(13) O(1)−Gd(1)−O(6d) 120.51(13)

O(2)−Gd(1)−O(3) 74.14(15) O(2)−Gd(1)−O(5) 130.66(15)

O(2)−Gd(1)−O(6) 86.92(14) O(2)−Gd(1)−O(7) 104.39(13)

O(2)−Gd(1)−O(8) 69.13(19) O(2)−Gd(1)−O(4d) 142.81(15)

O(2)−Gd(1)−O(6d) 139.64(13) O(3)−Gd(1)−O(5) 77.77(15)

O(3)−Gd(1)−O(6) 75.87(13) O(3)−Gd(1)−O(7) 138.81(15)

O(3)−Gd(1)−O(8) 137.80(18) O(3)−Gd(1)−O(4d) 131.59(12)

O(3)−Gd(1)−O(6d) 66.62(12) O(5)−Gd(1)−O(6) 124.06(13)

O(5)−Gd(1)−O(7) 72.86(16) O(5)−Gd(1)−O(8) 143.29(18)

O(5)−Gd(1)−O(4d) 85.27(15) O(5)−Gd(1)−O(6d) 49.26(12)

O(6)−Gd(1)−O(7) 145.10(14) O(6)−Gd(1)−O(8) 82.04(17)

O(6)−Gd(1)−O(4d) 77.14(13) O(6)−Gd(1)−O(6d) 75.02(13)

O(7)−Gd(1)−O(8) 71.95(19) O(7)−Gd(1)−O(4d) 74.14(13)

O(7)−Gd(1)−O(6d) 111.07(14) O(8)−Gd(1)−O(4d) 75.46(18)

O(8)−Gd(1)−O(6d) 140.13(16) O(4d)−Gd(1)−O(6d) 67.97(12)

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Symmetry transformation used to generate equivalent atoms: d: −1-x,−1−y,1−z

Figure S3. A: Coordination environment (ORTEP view drawn at the 30% probability level) around the

crystallographically equivalent metal ions Gd1 and Gd1_d and B: representation of the tricapped

trigonal-prismatic geometry for Gd1 (the capping atoms are O2, O7 and O6_d). Symmetry

transformation used to generate equivalent atoms: d, −1-x,−1−y,1−z

Figure S4. Different coordination modes observed for the N-BDC ligands. A: O,O’-carboxylato (red

ligand in Figure 2A); B: µ-O,O’-carboxylato (blue ligand in Figure 2A); C: µ-O,O,O’-carboxylato

(green ligand in Figure 2A).

Figure S5. Coordination environment (drawn at the 10% probability level) around the Gd1 atom of

modified MOF-LIC-1 after reaction with ethylisocyanate showing a coordinated ethylformamide

molecule (occupancy factor of 0.4 represented by dotted lines).

Figure S6. Steric restrictions around the amine groups belonging to the different types of N-BDC

ligands. A: O,O’-carboxylato N-BDC ligand (red ligand); B: µ-O,O’-carboxylato N-BDC ligand (blue

ligand); C: µ-O,O,O’-carboxylato N-BDC ligand (green ligand).

Table S4. Crystal data and structure refinement for MOF-LIC-1 modified with urethane functions

(MOF-LIC-F1).

Identification code MOF-LIC-F1

Empirical formula C19.70H25GdN4O8.90

Formula weight 617.49

Temperature 150(2) K

Wavelength 0.71073 Å

Crystal system Triclinic

Space group P−1 (No. 2)

Unit cell dimensions a = 10.5226(3) Å α = 100.129(2)°

b = 11.2071(4) Å β = 110.717(2)°

c = 12.8682(5) Å γ = 100.768(2)°

Volume 1345.19(8) Å3

Z 2

Density (calculated) 1.524 Mg/m3

Absorption coefficient 2.514 mm−1

F(000) 613

Crystal size 0.30 × 0.20 × 0.10 mm3

Theta range for data collection 4.1 to 29.1°

Index ranges −14<=h<=14, −15<=k<=15, −17<=l<=17

Reflections collected 29726 [R(int) = 0.0439]

Refinement method Full-matrix least-squares on F2

Data / parameters 6326 / 327

Goodness-of-fit on F2 1.101

R1 (wR2) [Fo>4σ(Fo)] R1 = 0.0389, wR2 = 0.1060

Largest diff. peak and hole 0.878 and −2.476 e.Å-3

Figure S7. Experimental (─) and theoretical (─) X-ray powder patterns for MOF-LIC-F1.

Table S5. Crystal data and structure refinement for MOF-LIC-1 modified with acetamide functions

(MOF-LIC-F2).

Identification code MOF-LIC-F2

Empirical formula C20H25.50GdN4O8.75

Formula weight 619.19

Temperature 150(2) K

Wavelength 0.78480 Å

Crystal system Triclinic

Space group P−1 (No. 2)

Unit cell dimensions a = 10.4926(6) Å α = 101.079(2)°

b = 11.2193(7) Å β = 110.206(2)°

c = 12.7812(8) Å γ = 99.870(2)°

Volume 1338.70(14) Å3

Z 2

Density (calculated) 1.536 Mg/m3

Absorption coefficient 3.266 mm-1

F(000) 615

Crystal size 0.40 × 0.17 × 0.10 mm3

Theta range for data collection 3.68 to 33.09°

Index ranges −14<=h<=14, −15<=k<=15, −17<=l<=17

Reflections collected 12052 [R(int) = 0.0429]

Refinement method Full-matrix least-squares on F2

Data / parameters 6441 / 397

Goodness-of-fit on F2 1.045

R1 (wR2) [Fo>4σ(Fo)] R1 = 0.0469, wR2 = 0.1260

Largest diff. peak and hole 2.409 and −2.037 e.Å-3

Figure S8. Experimental (─) and theoretical (─) X-ray powder patterns for MOF-LIC-F2.

Figure S9. Theoretical X-ray diffraction patterns for MOF-LIC-1, MOF-LIC-F1 and MOF-LIC-F2.