Supporting information for

Tuning porosity via control of interpenetration in a zinc isonicotinate metal organic framework

SHYAMAPADA NANDI and RAMANATHAN VAIDHYANATHAN*

Department of Chemistry, Indian Institute of Science Education and Research, Pune 411008, India

Analytical characterizations:

Powder X-ray diffraction:

Powder XRDs were carried out using a Rigaku Miniflex-600 instrument and processed using PDXL software.

Thermogravimetric Analysis:

Thermogravimetry was carried out on NETSZCH TGA-DSC system (Jupiter). The routine TGAs were done under N2 gas flow (20ml/min) (purge + protective) and samples were heated from RT to 550C at 10K/min.

IR spectroscopy:

IR spectra were obtained using a Nicolet ID5 attenuated total reflectance IR spectrometer operating at ambient temperature. The KBr pellets were used.

Structural figures:

Figure S1: Space-fill representation of the three-dimensional diamondoid network of 1 showing the three channels along a-, b- and c-axes. These have dimensions, 10.4 x 11.1Å; 10.2 x 12.1 Å; 11.5 x11.5 Å respectively. Note that these representations do not include the interpenetration.

Figure S2. The mean planes corresponding to the cyclohexyl faces of the adamantane units of three independent nets in 1 and 2 have been defined and the centroids have been indicated as balls. Note the adamantane units are highly distorted in 2 compared to 1, contrastingly the angles associated with the tetrahedrally positioned centroids are lot more symmetrical in 2 compared to 1. For 1: 112.719(4) x 118.124(5) x 99.462(2) x 115.245(5) x 112.719(5) x 99.462(2); For 2: 91.852(1) X 119.604(2) X 121.051(2) X 86.783(1) X 119.666(1) X 121.105(1).

Figure S3. SEM images of top: As made crystals of 1, bottom: Post-combustion phase, 3.

Figure S4. PXRD of 3 and 4 showing semi-crystalline powder (Carbon) with mesoporous profile.

Figure S5. BET Surface for 3 using 77K N2 isotherm showing the surface area 765 m2/g.

Figure S6. Pore size distribution of 3(using 77 K N2 isotherm and DFT modeled) showing an hierarchy of pores in the micro and mesoporous regimes.

FigureS7. UV Spectra of 1 and 3.The ZnO containing carbon phase, 3, has the 380nm peak characteristic of ZnO.

Figure S8. IR spectra of 1and 2. Selected peaks: C=O stretch: 1680cm-1; C-N stretch = 1460cm-1; aromatic ring = 500-1000cm-1. Other peaks (KBr Pellet): 3277(br, s), 1665(vs), 1608(vs), 1581(s), 1561(s), 1555(s), 1536(vs), 1421(vs), 1370(vs), 773(s), 693(vs). (Source: Infrared and Raman Spectra of Inorganic and CoordinationCompounds, Part B, Applications in Coordination, Organometallic, and Bioinorganic Chemistry, 6th Edition, Kazuo Nakamoto)

Figure S9. IR spectra of 3 showing characteristic ZnO IR spectra.

Ref: Beilstein J. Nanotech. Vol.5, Page: 402 (2014)

Table S1.

Metal salt / Solvent / Condition / Product
Zn Acetate / DMF (5mL) / 90oC for 3 days / Phase-2
Zn Acetate / DMF (3.5mL)+MeOH(2ml) / 90oC for 3 days / Phase1+Phase-2
Zn Acetate / DMA (3.5mL)+MeOH(2ml) / 90oC for 3 days / Phase-2
Zn Acetate / DMA(3.5ml)+MeOH (2mL)+ TEA (0.05mL) / 90oC for 3 days / Phase-2
Zn Acetate / DMA (3.5ml) + MeOH (2mL) / 120oC for 3 days / Phase-2
Zn Acetate / DMF(3.5ml)+MeOH(2ml) / 120oC for 3 days / Phase-2
Zn Acetate / DMF(3.5ml)+ CAN (2ml) / 120oC for 3 days / Phase-2
Zn Acetate / DMF (3.5ml) + MeOH (2mL) / 85oC for 3 days / Phase 1
Zn Acetate / DMF(3.5ml)+ CAN (2ml) / 85oC for 3 days / Phase 1
Zn Carbonate / Water(3ml)+MeOH(2ml) / 180oC for 3 days / Phase-2
Zn sulphate / Water(3ml)+EtOH(2ml) / 180oC for 3 days / Phase-2
Zn Acetate / DMF(3.5ml)+MeOH(2ml) / 90oC for 1 day / Phase-1
Zn Acetate / DMF(3.5ml)+EtOH(2ml) / 90oC for 1 day / Phase-1

TEA- Triethylamine

Temperature below 90oC Phase-1 is favorable. Above 90oC phase-2 is favorable.