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1 DOI: /NCHEM.2045 Capturing Snapshots of Post-synthetic Metallation Chemistry in Metal Organic Frameworks Witold M. Bloch 1, Alexandre Burgun 1, Campbell J. Coghlan 1, Richmond Lee 2, Michelle L. Coote 2, Christian J. Doonan 1*, Christopher J. Sumby 1* 1. School of Chemistry and Physics, Centre for Advanced Nanomaterials, The University of Adelaide, Adelaide, SA 5005, Australia. 2. Research School of Chemistry, Australian National University, Canberra, ACT 0200, Australia NATURE CHEMISTRY 1

2 Contents 1. Experimental section Materials and measurements Synthetic Methods Gas adsorption measurements Infrared Spectroscopy Thermogravimetric analysis X-ray crystallography Thermal Ellipsoid Plots for all structures at the 50% probability level Specific details of each refinement Selected details of data collections and structure refinements Refinement of thermal parameters for metalated species CSD comparison of the metal-ligand bond lengths Structural contraction of 1 1-des Metalation experiments Powder X-ray diffraction Gas adsorption measurements Energy dispersive X-ray spectroscopy (EDX) Inductively coupled plasma mass spectrometry (ICPMS) Metalation of 1 with cobalt chloride F obs electron density maps General procedures Theoretical study of reaction mechanism Theoretical procedures Detailed theoretical results Cartesian coordinates References NATURE CHEMISTRY 2

3 1. Experimental section 1.1. Materials and measurements Unless otherwise stated, all chemicals were obtained from commercial sources and used as received. Acetonitrile was distilled from CaH 2 and degassed with Ar. LH 2 was prepared by a previously reported procedure. 1 Elemental analyses were performed by the Campbell Microanalytical Laboratory at the University of Otago (North Dunedin, New Zealand). Infrared spectra were collected on a Perkin-Elmer Spectrum 100 using a UATR sampling accessory. Thermal gravimetric analysis (TGA) was performed on a Perkin-Elmer STA-6000 instrument under a constant flow of N 2 at a temperature increase rate of 10 C/min. Powder X-ray diffraction data were collected on a Bruker Advanced D8 diffractometer (capillary stage) using Cu Kα radiation (λ = Å, 50 kw/40ma). Simulated powder X-ray diffraction patterns were generated from the single crystal data using Mercury 3.0. Energydispersive X-ray spectroscopy (EDX) was performed on a Philips XL30 field emission scanning electron microscope. Inductively coupled plasma mass spectrometry was performed on a Solution 7500cs ICPMS spectrometer Synthetic Methods Synthesis of [Mn 3 (L) 2 (L )] xs (1 xs). In a screw cap vial, MnCl 2 4H 2 O (24.7 mg, 0.12 mmol) and L (31.6 mg, 0.07 mmol) were combined and dissolved in DMF (4 ml) and water (2 ml). The mixture was heated at 100 C for 2 days resulting in colorless rhombus-shaped crystals. The crystals were washed in DMF ( 3), methanol ( 5) and heated under vacuum at 100 C for 1 h to yield the activated sample 1-des (24.0 mg, 66% based on analysis); ν max (neat, cm -1 ): 1606 (s, C=O), 1555 (m, C=C), 1508(w, C=C), 1406, (s); Found C 58.8, H 4.7, N 11.0, C 75 H 66 N 12 O 12 Mn H 2 O requires C 58.8, H 4.6, N 11.0%. [Mn 3 (L) 2 Co(L )(H 2 O) 4 ]Cl 2 (1 [Co(H 2 O) 4 ]Cl 2 ). The as-synthesized material, 1 (24.0 mg), was solvent exchanged with methanol. The solvent was replenished 7 times and the crystals were allowed to soak in methanol for 10 minutes in between each wash. CoCl 2 6H 2 O (30.0 mg) was added to the vial containing 1 xch 3 OH and the resulting mixture was placed in an oven pre-set at 65 C for 16 h. The blue suspension was then allowed to cool to room temperature, and the solvent was exchanged for fresh methanol ( 7). The solvent was decanted, and the wet crystals (1 [Co(H 2 O) 4 ]Cl 2 ) were subject to a flow of N 2 for 1 h. NATURE CHEMISTRY 3

4 ν max (neat, cm -1 ): 3340 (s, br, H 2 O), 1603 (s, C=O), 1552 (m, C=C), 1509 (w, C=C), 1405 (s). The pink sample was activated by heating at 100 C under vacuum for 1 h to yield blue crystals of 1 [CoCl 2 ]. ν max (neat, cm -1 ) 1606 (s, C=O), 1549 (m, C=C), 1509 (w, C=C), Found C 51.6, H 4.8, N 9.6, C 75 H 74 N 12 O 16 Mn 3 CoCl 2 3H 2 O (1 [Co(H 2 O) 4 ]Cl 2 3H 2 O) requires C 51.5, H 4.6, N 9.6%. [Mn 3 (L) 2 Co(L )Cl 2 ] (1 [CoCl 2 ]). 1 [Co(H 2 O) 4 ]Cl 2 was heated at 100 C under vacuum for 1 h to obtain 1 [CoCl 2 ] (activated sample). Crystals suitable for X-ray crystallography were obtained by heating the sample in-situ under nitrogen flow on the diffractometer (100 C) or immersing crystals of 1 [Co(H 2 O) 4 ]Cl 2 in distilled acetonitrile. ν max (neat, cm -1 ): 1606 (s, C=O), 1549 (m, C=C), 1509 (m, C=C), 1405 (s), 1304 (s). [Mn 3 (L) 2 Rh(L )(CO) 2 Rh(CO) 2 Cl 2 ] (1 [Rh(CO) 2 ][Rh(CO) 2 Cl 2 ]). The as-synthesized material, 1 (24.0 mg), was solvent exchanged with distilled and freshly degassed acetonitrile. The solvent was replenished 7 times, and the crystals were allowed to soak for 10 minutes in between each wash. [Rh(CO) 2 Cl] 2 (30.0 mg) was added to the vial and the resulting mixture was allowed to stand at room temperature for 48 h. The resulting bright yellow crystals were then washed with distilled and freshly degassed acetonitrile ( 7). The solvent was decanted, and the wet crystals were subject to a flow of N 2 for 1 h. The material was then heated at 110 C under vacuum for 2 h to obtain 1 [Rh(CO) 2 ][Rh(CO) 2 Cl 2 ] (activated sample). ν max (neat, cm -1 ): 2106 (m, CO), 2075 (m, CO), 2046 (m, CO), 2033 (m, CO), 2002 (m, CO), 1611 (s, C=O), 1557 (m, C=C), 1510 (m, C=C), 1406 (s), 1303 (s); Found C 48.02, H 3.92, N 8.79, C 79 H 66 Cl 2 N 12 O 12 Mn 3 Rh 2 8H 2 O requires C 48.38, H 4.21, N 8.57%. [Mn 3 (L) 2 Rh(L )(H 2 O) 4 Cl 3 )] (1 [Rh(H 2 O) 4 ]Cl 3 ). Method A: Crystals of 1 [Rh(CO) 2 ][Rh(CO) 2 Cl 2 ] were allowed to stand in a 1:1 solution of methanol/water at room temperature for 3 months. The resulting yellow crystals were washed with fresh methanol ( 5) and characterized by single crystal X-ray diffraction to obtain 1 [Rh(H 2 O) 4 ]X 3. Method B: The as-synthesized material, 1 (24.0 mg), was solvent exchanged with methanol, replenishing the solvent 7 times and allowing the crystals to soak for 10 minutes in between each wash. [Rh(CO) 2 Cl] 2 (30.0 mg) was added to the vial and the resulting mixture was allowed to stand at room temperature for 48 h. Washing the resulting material with methanol ( 7) gave 1 [Rh(H 2 O) 4 ]Cl 3 as yellow crystals. ν max (neat, cm -1 ): 3371 (s, br H 2 O), 1605 (s, NATURE CHEMISTRY 4

5 C=O), 1553 (m, C=C), 1508 (m, C=C), 1406 (s), 1305 (s). The solvent was decanted, and the wet crystals were subject to a flow of N 2 for 1 h. The material was then heated at 110 C under vacuum for 2 h to obtain 1 [Rh(H 2 O) 4 ]Cl 3 (activated sample). Found C 46.56, H 4.66, N 8.57, C 75 H 74 Cl 3 N 12 O 16 Mn 3 Rh 1 9H 2 O requires C 46.54, H 4.79, N 8.68%. [Mn 3 (L) 2 Rh(L )(CO)(CH 3 CN)(COMe)(I)I] (1 [Rh(CO)(CH 3 CN)(COMe)I]I). Methyl iodide was introduced to a dry acetonitrile solution containing crystals of 1 [Rh(CO) 2 ][Rh(CO) 2 Cl 2 ] by vapour diffusion. After 48 h at room temperature, the resulting bright orange crystals were washed with distilled and freshly degassed acetonitrile ( 7) to give 1 [Rh(CO)(CH 3 CN)(COMe)I]I. ν max (neat, cm -1 ): 2072 (m, CO), 1716 (m, COMe), 1609 (s, -CO 2 ), 1554 (m, C=C), 1510 (m, C=C), 1408 (s), 1304 (s) Gas adsorption measurements Gas adsorption isotherm measurements were performed on an ASAP 2020 Surface Area and Pore Size Analyser. Activation of samples was carried out as described in supplementary table 5. UHP grade (99.999%) N 2 and CO 2 were used for all measurements. The temperatures were maintained at 77 K (liquid nitrogen bath or cryo-cooler circulator) NATURE CHEMISTRY 5

6 2. Infrared Spectroscopy Supplementary Figure 1. IR spectra of 1 [Rh(CO) 2 ][RhCl 2 (CO) 2 ] and 1 [Rh(CO)(CH 3 CN)(COMe)I]I in the range cm -1. NATURE CHEMISTRY 6

7 3. Thermogravimetric analysis Supplementary Figure 2. a) TGA trace of an as-synthesized sample of 1. The weight loss of 64% corresponds to solvent molecules lost from the pores of the material; b) TGA trace of a sample of 1-des. The weight loss of 4% is equated to 3.5 H 2 O molecules being lost from the pores (adsorbed during sample preparation). The MOF is thermally stable up to ~425 C. NATURE CHEMISTRY 7

8 Supplementary Figure 3. a) TGA trace of an as-synthesized sample of 1 [Co(H 2 O)]Cl 2. The weight loss of 28% corresponds to methanol solvent molecules lost from the pores of the material; b) TGA trace of a sample of 1 [CoCl 2 ] obtained by heating 1 [Co(H 2 O)]Cl 2 at 100 C for 1 h. The weight loss of 3% is equated to 3 H 2 O molecules being lost from the pores (adsorbed during sample preparation), thus, initially, some portion of the material is present as 1 [Co(H 2 O)]Cl 2. The Co metalated MOF is thermally stable up to ~360 C. NATURE CHEMISTRY 8

9 4. X-ray crystallography 4.1. Thermal Ellipsoid Plots for all structures at the 50% probability level Supplementary Figure 4. The asymmetric unit of 1 DMF, with all non-hydrogen atoms shown as ellipsoids at the 50% probability level. Supplementary Figure 5. The asymmetric unit of 1-des, with all non-hydrogen atoms shown as ellipsoids at the 50% probability level. NATURE CHEMISTRY 9

10 Supplementary Figure 6. The asymmetric unit of 1 [Co(H 2 O) 4 ]Cl 2, with all non-hydrogen atoms shown as ellipsoids at the 50% probability level. Supplementary Figure 7. The asymmetric unit of 1 [CoCl 2 ], with all non-hydrogen atoms shown as ellipsoids at the 50% probability level. NATURE CHEMISTRY 10

11 Supplementary Figure 8. The asymmetric unit of 1 [Rh(CO) 2 ][Rh(CO) 2 Cl 2 ], with all nonhydrogen atoms shown as ellipsoids at the 50% probability level. Supplementary Figure 9. The asymmetric unit of 1 [Rh(OH 2 ) 4 ]Cl 3, with all non-hydrogen atoms shown as ellipsoids at the 50% probability level. NATURE CHEMISTRY 11

12 Supplementary Figure 10. The asymmetric unit of 1 [Rh(CO)(CH 3 CN)(COMe)I]I, with all atoms except hydrogen atoms and the acetyl group atoms shown as ellipsoids at the 50% probability level. NATURE CHEMISTRY 12

13 4.2. Specific details of each refinement Structure of 1: The structure has large solvent accessible voids. These contained a number of diffuse electron density peaks that could not be adequately identified and refined as solvent. The SQUEEZE routine of PLATON was applied to the collected data, which resulted in significant reductions in R 1 and wr 2 and an improvement in the GOF. R 1, wr 2 and GOF before SQUEEZE routine: 17.17%, 52.54%, 2.319; after SQUEEZE routine: 5.65%, 17.02%, The contents of the solvent region calculated from the result of SQUEEZE routine equates to 8 DMF molecules. Structure of 1-des: This structure contains solvent accessible voids but, due to the desolvation of the framework, does not contain any significant electron density. Use of the SQUEEZE routine was not justified. Structure of 1 [Co(H 2 O) 4 ]Cl 2 : The structure has large solvent accessible voids. Within these voids, one half-occupied chloride ion was unambiguously located (positioned on a mirror plane), while the other half chloride ion was assigned over two positions (0.25 2) based on chemical sensibility and location. The void channels contained a number of other diffuse electron density peaks that could not be adequately identified and refined as solvent. The SQUEEZE routine of PLATON was applied to the collected data, which resulted in significant reductions in R 1 and wr 2 and an improvement in the GOF. R 1, wr 2 and GOF before SQUEEZE routine: 19.31%, 52.41% and 1.960; after SQUEEZE routine: 9.38%, 24.70% and The contents of the solvent region calculated from the result of SQUEEZE routine equates to 9 methanol molecules. Structure of 1 [CoCl 2 ]: The structure has large solvent accessible voids. These contained a number of diffuse electron density peaks that could not be adequately identified and refined as solvent. The SQUEEZE routine of PLATON was applied to the collected data, which resulted in significant reductions in R 1 and wr 2 and an improvement in the GOF. R 1, wr 2 and GOF before SQUEEZE routine: 14.53%, 44.17%, 1.718; after SQUEEZE routine: 7.76%, 21.81%, The contents of the solvent region calculated from the result of SQUEEZE routine equates to 19 acetonitrile molecules. NATURE CHEMISTRY 13

14 Structure of 1 [Rh(CO) 2 ][RhCl 2 (CO) 2 ]: The diffrn_measured_fraction_theta_full is low (91.8%). This is low due to the constraints of the goniometer (phi rotation) and the orientation of the crystal during this particular data collection. It is not possible to remove and remount crystals of this sample following a data collection at 100K (the crystal collapse upon warming). Datasets with better completeness have been obtained but the quality of these crystals were lower and provided a less satisfactory refinement. The SQUEEZE routine of PLATON was applied to the collected data, which resulted in slight reductions in R 1 and wr 2 but no change in the GOF. R 1, wr 2 and GOF before SQUEEZE routine: 7.93%, 24.95%, 1.032; after SQUEEZE routine: 7.49%, 23.21%, The contents of the solvent region calculated from the result of SQUEEZE routine equates to 3 acetonitrile molecules. Structure of 1 [Rh(H 2 O) 4 ]Cl 3 : The ratio of the given and expected molecular weight differ as based on elemental analysis the formula was modified to include anions not located in the difference map. This addition of chloride anions in line with the residual election density removed using the squeeze routine. The SQUEEZE routine of PLATON was applied to the collected data, which resulted in slight reductions in R 1 and wr 2 but no change in the GOF. R 1, wr 2 and GOF before SQUEEZE routine: 12.31%, 39.57%, 1.624; after SQUEEZE routine: 7.50%, 23.31%, The contents of the solvent region calculated from the result of SQUEEZE routine equates to 15 methanol molecules, in addition to the 6 chloride anions (3 per Rh). Structure of 1 [Rh(CO)(CH 3 CN)(COMe)I]I: A number of restraints (18) were used to allow the structure to be adequately refined. The largest peak in the difference map is located adjacent to a partially occupied iodide counterion residing in the pores of the MOF. For the post-synthetically added Rh moiety of the structure further restraints and constraints were employed. The I ligand is disordered over two positions corresponding to reaction with the Rh from above or below; both sites were refined with an occupancy set at 0.25 (these are on the mirror plane). The CO(Me) group is also disordered over these same two positions. Due to the significant electron density associated with the iodide anions these atoms could not be definitely identified in the difference map or refined and were placed in calculated positions with chemically sensible bond lengths and angles; an AFIX 1 command was used (i.e. the coordinates, s.o.f. and U are fixed [at 0.15]). The CO and CH 3 CN ligands are also disordered over the mirror plane and thus occupy the same site. These were refined with a combination of DFIX restraints (3) and EADP and EXYZ restraints. Unfortunately, this approach results NATURE CHEMISTRY 14

15 in an averaging of bond lengths for these atom positions (specifically the parameters involving Rh, N/C and C/O). ISOR restraints were used for C92 and O95 (the CO ligand). One site for the non-coordinated iodine counterion was located in the pores and this was refined with occupancy of 0.25 (on a mirror plane). Additional sites for this iodine anion could not be definitively located and half an iodide anion was included in the formula. The SQUEEZE routine of PLATON was applied to the collected data, which resulted in improvements in R 1, wr 2 and the GOF. R 1, wr 2 and GOF after SQUEEZE routine: 10.76%, 32.71%, The contents of the solvent region calculated from the result of SQUEEZE routine equates to 9.5 acetonitrile molecules, in addition to the iodide anion not found in the difference map (0.25 per Rh). NATURE CHEMISTRY 15

16 4.3. Selected details of data collections and structure refinements Supplementary Table 1. X-ray experimental data for 1 DMF, 1-des, 1 [Co(H 2 O) 4 ]Cl 2, and 1 [CoCl 2 ]. Compound 1 DMF 1-des 1 [Co(H 2 O) 4 ]Cl 2 1 [CoCl 2 ] Empirical formula C 75 H 66 N 12 O 12 Mn 3 C 75 H 66 N 12 O 16 Mn 3 C 75 H 70 N 12 O 16 Mn 3 CoCl 2 C 150 H 132 N 24 O 24 Mn 6 Co 2 Cl 4 Formula weight Crystal system Monoclinic Monoclinic Monoclinic Monoclinic Space group P2 1 /c C2/c P2 1 /m P2 1 /c a (Å) (3) (10) (12) (2) b (Å) (7) (7) (3) (7) c (Å) (5) (2) (16) (10) α (º) β (º) 93.57(3) (6) (11) 94.19(3) γ (º) Volume (Å 3 ) 10291(4) (9) (9) 21219(7) Z Density (calc.) (Mg/m 3 ) Absorption coefficient (mm -1 ) F(000) Crystal size (mm 3 ) θ range for data collection (º) 1.01 to to to to Reflections collected Observed reflections [R(int)] [0.0625] 9635 [0.1103] [0.0916] [0.1222] Data/restraints/parameters 27582/0/ /0/ /0/ /0/1946 Completeness (%) Goodness-of-fit on F R 1 [I>2σ(Ι)] wr 2 (all data) Largest diff. peak and hole (e.å -3) and and and and NATURE CHEMISTRY 16

17 Supplementary Table 2. X-ray experimental data for 1 [Rh(CO) 2 ][RhCl 2 (CO) 2 ], 1 [Rh(H 2 O) 4 ]Cl 3, and 1 [Rh(CO)(CH 3 CN)(COMe)I]I. Compound 1 [Rh(CO) 2 ][RhCl 2 (CO) 2 ] 1 [Rh(H 2 O) 4 ]Cl 3 1 [Rh(CO)(CH 3 CN)(COMe)I]I Empirical formula C 79 H 66 Cl 2 Mn 3 N 12 O 16 Rh 2 C 75 H 66 Cl 3 Mn 3 N 12 O 16 Rh C 80 H 72 I 2 Mn 3 N 13 O 14 Rh Formula weight Crystal system Monoclinic Monoclinic Monoclinic Space group P2 1 /m P2 1 /m P2 1 /m a (Å) (3) (3) (5) b (Å) (7) (7) (15) c (Å) (3) (3) (6) α (º) β (º) 96.63(3) 96.42(3) (4) γ (º) Volume (Å 3 ) (19) (18) (4) Z Density (calc.) (Mg/m 3 ) Absorption coefficient (mm -1 ) F(000) Crystal size (mm 3 ) θ range for data collection (º) 1.66 to to to Reflections collected Observed reflections [R(int)] 9702 [0.0284] [0.0760] [ ] Data/restraints/parameters 9702/0/ /0/ /14/518 Completeness (%) Goodness-of-fit on F R 1 [I>2σ(Ι)] wr 2 (all data) Largest diff. peak and hole (e.å -3) and and and NATURE CHEMISTRY 17

18 4.4. Refinement of thermal parameters for metalated species Supplementary Table 3: Refined site occupancy factors of the post-synthetically inserted metal ions in MOF 1. Structure Atom refined Refined Occupancy 1 [Co(H 2 O) 4 ]Cl 2 Co a 1 [CoCl 2 ] Co b 1 [Rh(CO) 2 ][Rh(CO) 2 Cl 2 ] Rh a 1 [Rh(H 2 O) 4 ]Cl 3 Rh a 1 [Rh(CO)(CH 3 CN)(COMe)I]I Rh a a metal ion located on a crystallographic mirror plane. b average over two crystallographically unique sites. NATURE CHEMISTRY 18

19 4.5. CSD comparison of the metal-ligand bond lengths To support the assignment of the surrounding ligands in the post-synthetically metalated species of 1, histograms plotting Co-O, Co-Cl, Rh-O, Rh-Cl, and Rh-I bond lengths from CSD searches (CSD version 5.35, release date November 2013). Supplementary Figure 11: A histogram showing a comparison of Co-O and Co-Cl bond lengths for structures deposited in the CSD (CSD version 5.35, release date November 2013). Co-O bond lengths found in 1 [Co(H 2 O) 4 ]Cl 2 fall within the range of a Co-O bond, but are outside of a Co-Cl bond length. Co-Cl bond lengths found in 1 [CoCl 2 ] are within the normal range for Co-Cl bond lengths. NATURE CHEMISTRY 19

20 Supplementary Figure 12. A histogram showing a comparison of Rh-Cl and Rh-I bond lengths for structures deposited in the CSD (CSD version 5.35, release date November 2013). The Rh-I bond length found in 1 [Rh(CO)(CH 3 CN)(COMe)I]I is outside the range of a Rh-Cl bond, but within the range of a Rh-I bond. NATURE CHEMISTRY 20

21 5. Metalation experiments Supplementary Table 4. Metalation conditions for 1. Metal salt CoCl 2 6H 2 O CuCl 2 2H 2 O Zn(NO 3 ) 2 6H 2 O Cd(NO 3 ) 2 3H 2 O [Rh(CO) 2 Cl] 2 Conditions 65 C, 1 day, MeOH 4 C, 3 days, EtOH r.t., 2 days, CH 3 CN r.t., 2 days, CH 3 CN r.t., 2 days, MeOH [Rh(CO) 2 Cl] 2 *Dry solvent under argon. r.t., 2 days, CH 3 CN* Supplementary Figure 13. Photo images of 1 [Rh] showing colour changes after reaction with MeI; (left) crystals of 1 [Rh(CO) 2 ][Rh(CO) 2 Cl 2 ]; (right) crystals of 1 [RhI(COMe)(CO)(CH 3 CN)]I. NATURE CHEMISTRY 21

22 6. Powder X-ray diffraction Supplementary Figure 14. PXRD patterns of (a) 1 DMF simulated (black); (b) 1 DMF (blue); (c) 1-des simulated (purple); (d) 1-des (red). NATURE CHEMISTRY 22

23 Supplementary Figure 15. Experimental PXRD patterns of (a) 1 DMF; (b) 1 [Co(H 2 O) 4 ]Cl 2 ; (c) 1 [CoCl 2 ]; (d) 1 [Rh(CO) 2 ][Rh(CO) 2 Cl 2 ]; (e) 1 [Rh(H 2 O)4]Cl 3 ; (f) 1 [Rh(CO)(CH 3 CN)(COMe)I]I. Supplementary Figure 16. Experimental PXRD patterns of (a) 1 DMF; (b) 1 [Cu]; (c) 1 [Zn]; (d) 1 [Cd]. NATURE CHEMISTRY 23

24 7. Structural contraction of 1 1-des Supplementary Figure 17. a) The structure of 1 DMF viewed along the c axis; b) the structure of 1-des viewed along the a axis. c) Bridging ligand L in 1 DMF, selected lengths [Å] and angles [ ]: C24-C , C24-C1-C d) Bridging ligand L in 1-des, selected lengths [Å] and angles [ ]: C64-C64A 13.79, C64-C2-C64A NATURE CHEMISTRY 24

25 Supplementary Figure 18. a) A perspective view a 2-D layer of 1 DMF, ligand L (connection to give a 3-D structure) omitted for clarity. b) A perspective view of 1-des, ligand L omitted for clarity. c) Coordinated ligand L in 1 DMF, selected lengths [Å] and angles [ ]: C64-C , C64-C2-C ; d) coordinated ligand L in 1-des, selected lengths [Å] and angles [ ]: C24-C , C24-C1-C NATURE CHEMISTRY 25

26 8. Gas adsorption measurements Supplementary Figure 19. N 2 77 K isotherms of 1-des (blue circles). The flexibility (gating) of the material can be seen in an enlargement of the low pressure region. Supplementary Figure 20. N 2 77 K isotherms of 1 [CoCl 2 ] (blue circles), 1 [Rh(H 2 O) 4 ]Cl 3 (orange circles), and 1 [Rh(CO) 2 ][RhCl 2 (CO) 2 ] (royal blue). NATURE CHEMISTRY 26

27 Supplementary Table 5. Activation conditions and BET surface areas for 1-des, 1 [CoCl 2 ], 1 [Rh(CO) 2 ][RhCl 2 (CO) 2 ], 1 [Rh(H 2 O) 4 ]Cl 3. MOF Activation conditions BET surface area (m 2 g -1 ) 1-des MeOH, 1 h, 100 C [CoCl 2 ] MeOH, 1 h, 100 C [Rh(CO) 2 ][RhCl 2 (CO) 2 ] CH 3 CN, 1 h, 110 C [Rh(H 2 O) 4 ]Cl 3 CH 3 CN, 1 h, 110 C 845 Supplementary Figure 21. Derivation of the BET surface area from the 77 K N 2 adsorption isotherms a) 1-des; b) 1 [CoCl 2 ]; c) 1 [Rh(CO) 2 ][RhCl 2 (CO) 2 ]; d) 1 [Rh(H 2 O) 4 ]Cl 3. NATURE CHEMISTRY 27

28 9. Energy dispersive X-ray spectroscopy (EDX) Supplementary Table 6. Extent of metalation as determined by EDX for 1 [CoCl 2 ] and 1 [Rh(CO)(CH 3 CN)(COMe)I]I. MOF Mn(II) a Metal ion b Halide counter ion c 1 [CoCl 2 ] ± ± [Rh(CO)(CH 3 CN)(COMe)I]I ± ±0.14 a Normalized according to the Mn3 metal node in the structure of 1. b Average atomic % obtained from three areas and three crystals; Co(II) for 1 [CoCl2 ], Rh(III) for 1 [Rh(CO)(CH 3 CN)(COMe)I]I c Average atomic % obtained from three areas and three crystals; Cl for 1 [CoCl2 ], I for 1 [Rh(CO)(CH 3 CN)(COMe)I]I Supplementary Figure 22. Examples of raw EDX spectra. (a) 1 [CoCl 2 ]; (b) 1 [RhI(COMe)(CO)(CH 3 CN)]I. NATURE CHEMISTRY 28

29 Supplementary Figure 23. SEM images of 1-metalated; (a) an example of a single crystal; (b) an example of an area of crystals used for analysis. NATURE CHEMISTRY 29

30 10. Inductively coupled plasma mass spectrometry (ICPMS) Metalation of 1 with cobalt chloride Metalation of 1 with CoCl 2 6H 2 O was carried out in methanol at 65 C. At the desired time, the reaction sample was quenched by exchange with fresh methanol and the allowed to cool to room temperature. Subsequent to the ICP-MS measurements, samples were washed five times with fresh methanol and dried under high vacuum. Supplementary Figure 24. A plot showing the time-dependant metalation of 1 with of CoCl 2. Each point represents an average value of three samples taken at that particular time. The error bars represent the standard deviation. NATURE CHEMISTRY 30

31 11. F obs electron density maps General procedures F obs electron density maps where generated using ShelXle with the following settings: map precision = 5; factor to down weight weak data = 1; F obs map = 1.41 eå 3, map radius Å (from the Rh centre); map truncation type = sphere/around rotation centre (i.e. Rh atom); line transparency 0.8; line width = 0.5. Supplementary Figure 25. F obs electron density maps (left) and corresponding crystal structure fragments (right) for the metalated Rh(III) species in 1 [Rh(H 2 O) 4 ]Cl 3 ; a) top view; b) side view; c) front view. Additional electron density in the above images originates from framework atoms. (* denotes symmetry generated atoms). NATURE CHEMISTRY 31

32 Supplementary Figure 26. F obs electron density maps for the metalated Rh(III) centre in two examples of 1 [Rh(CO)(CH 3 CN)(COMe)I]I (left and middle) and the corresponding crystal structure fragments as assigned; a) and d) top view; b) and e) side view; c) and f) front view. Additional electron density in the above images originates from framework atoms. The electron density corresponding to the lower axial COMe ligand (O101, C100, C102) can be clearly observed in b) and e). The upper axial COMe group (C105, C104, O106) appears to be distorted as observed in c) and f). (* denotes symmetry generated atoms). NATURE CHEMISTRY 32

33 12. Theoretical study of reaction mechanism Theoretical procedures Density functional theory studies were carried out with the Gaussian 09 2 suite of programs. Geometries of gas phase minimum and transition state electronic structures were optimised using the Minnesota meta hybrid functional M11-L 3,4 with Stuttgart-Dresden effective core potential SDD 5,6 for Rh and I atoms and Pople s basis set 6-31G(d,p) 7-9 for rest of the atoms. Frequency calculations were carried out at that level to ensure convergence (all positive eigenvalues for minima and single negative for saddle points). Thermochemical corrections and zero point vibrational energies, as well as the infrared spectra, were determined at the gas phase M11-L/6-31G(d,p)+SDD level using the unscaled frequencies. The solvation energies, for acetonitrile solution, were calculated as singlet points on the gas-phase optimized structures. These calculations were performed using the SMD model 10. An additional correction term, ΔnRT ln(rt/p ) is included to account for passage of molecules from 1 atm to 1 mol/l in solution Detailed theoretical results The ligated Rh(I) is first involved in an S N 2 attack on MeI through TS-I (ΔH soln = kcal mol -1 ) to form the Rh(III) complex II (Figure SI 20). The presence of the counterion [Rh(Cl) 2 (CO) 2 ] - at the axial position in I is responsible for rendering the ligated Rh(I) center more nucleophilic. Electron donation by [Rh(Cl) 2 (CO) 2 ] - counterion onto the ligated Rh(I) to facilitate the S N 2 attack is evidenced by the shortening of the intermolecular Cl Rh bond length from (I) to (TS-I) and to Å (II). The intermediate II at this stage is 4.5 kcal mol -1 more endothermic than the starting materials. To drive the reaction forward, the subsequent 1,2-migratory insertion of the methyl group into the carbonyl requires an overall barrier of 18.1 kcal mol -1 to reach an exothermic minimum III (ΔH soln = kcal mol -1 ). Further dissociation of III into charged species IV and V in order to accommodate a solvent NATURE CHEMISTRY 33

34 molecule on IV is endothermic by 1.2 kcal mol -1. The addition of MeCN solvent molecule to the electron deficient cationic Rh(III) IV complex is a facile process (TS-III; activation barrier of kcal mol -1 ) yielding the solvated product VI. However to reach a more energetically stable state, the anion V is oxidized by another MeI through TS-IV to VII (ΔH soln = kcal mol -1 ). Recombination of VI and iodide and the concomitant explusion of VIII is further exothermic (ΔH soln = kcal mol -1 ). Supplementary Figure 27. SMD//M11-L/6-31G(d,p)+SDD calculations of the energy profile ( H soln, 298 K, kcal mol 1 ), along with the structures of the reactant and products. Simulated frequencies for 1 [Rh(CO) 2 ][RhCl 2 (CO) 2 ] (comparative experimental frequencies in parenthesis): symmetric C O stretch 2206 cm -1 (2106 cm -1 ); asymmetric C O stretch mode 2154 cm -1 (2046 cm -1 ). 1 [RhI(COMe)(CO)(CH 3 CN)]I: C O stretch 2227 cm -1 (2072cm -1 ); C=O stretch 1900 cm -1 (1716 cm -1 ). NATURE CHEMISTRY 34

35 Supplementary Figure 28. Computed structures of the reactant I (a) and product VI (b) showing only the atoms surrounding the Rh(I) and Rh(III) centre respectively. Supplementary Table 7. A comparison of key calculated bond lengths (Å) with the corresponding experimental values, which are shown in square brackets. Parameter I [1 [Rh(CO) 2 ][RhCl 2 (CO) 2 ]] VI [1 [RhI(COMe)(CO)(CH 3 CN)]I] Rh-CO 1.874, [1.844(11)] [1.948(11)] a Rh-N pyz 2.083, [2.078(5)] 2.045, [2.073(7)] Rh-C(O)Me b Rh-I [2.982(2) and 3.008(5)] c Rh-N CCH [1.948(11)] a C O [1.139(12)] [1.102(12)] a. EXYZ and EADP cards were required for the refinement of the C/N and O/C atoms at this site (CO/CH 3 CN disorder). Thus the bond lengths are averaged over the Rh-C/N O/C moiety and cannot be directly compared. b. The corresponding bond length in the structure was not refined as the group was added in a calculated position and refined with an AFIX 1 command. c. Bond lengths for the two positions of the disorder model for the I centre are given. In MOF 1 these are distinct chemical environments due to the structure of the extended framework. NATURE CHEMISTRY 35

36 12.3. Cartesian coordinates MeI C H H H I Electronic energy, E= Thermal correction to enthalpy, E corr = E solv = MeCN C H H H C N E= E corr = E solv = Iodide E= E corr = E solv = I I E= E corr = E solvation = C C C C C C C C C C C C C C C C C C C C C C C N N NATURE CHEMISTRY 36

37 N N Rh H H H H H H H H H H H H H H H H H H H H H H H H C C O O Rh C C O O Cl Cl TS-I E= E corr = E solvation = Imaginary freq.= i cm -1 C C C C C NATURE CHEMISTRY 37

38 C C C C C C C C C C C C C C C C C C N N N N Rh H H H H H H H H H H H H H C C O O Rh C C O O Cl Cl H C H H I NATURE CHEMISTRY 38

39 II E= E corr = E solv = C C C C C C C C C C C C C C C C C C C C C C C N N N N Rh H H H H H H H H H H H H H H H H H H H NATURE CHEMISTRY 39

40 H H H H H C C O O Rh C C O O Cl Cl H C H H I TS-II E= E corr = E solv = Imaginary freq= i cm -1 C C C C C C C C C C C C C C C C C C C C C C C N N NATURE CHEMISTRY 40

41 N N Rh H H H H H H H H H H H H H H H H H H H H H H H H C C O O Rh C C O O Cl Cl H C H H I III E= E corr = E solv = C C C C C C NATURE CHEMISTRY 41

42 C C C C C C C C C C C C C C C C C N N N N Rh H H H H H H H H H H H H H H H H H H H H H H H H C C O O Rh C C O O Cl Cl H C H H I NATURE CHEMISTRY 42

43 IV E= E corr = E solv = C C C C C C C C C C C C C C C C C C C C C C C N N N N Rh H H H H H H H H H H H H H H H H H H H H H H NATURE CHEMISTRY 43

44 H H C C O O I H C H H V E= E corr = E solv = Rh C C O O Cl Cl TS-III E= E corr = E solv = Imaginary freq.= 64.91i cm -1 C C C C C C C C C C C C C C C C C C NATURE CHEMISTRY 44

45 C C C C C N N N N Rh H H H H H H H H H H H H H H H H H H H H H H H H C C O O I H C H H N C C H H H VI E= E corr = E solv = C C C NATURE CHEMISTRY 45

46 C C C C C C C C C C C C C C C C C C C C N N N N Rh H H H H H H H H H H H H H H H H H H H H H H H H C C O O I H C H H N C C H H H NATURE CHEMISTRY 46

47 TS-IV E= E corr = E solv = Imaginary freq.= i cm -1 Rh C C O O Cl Cl C H H H I VII E= E corr = E solv = Rh C C O O Cl Cl H C H H I VIII E= NATURE CHEMISTRY 47