Supramolecular frameworks based on [60]fullerene hexakisadducts

[60]Fullerene hexakisadducts possessing 12 carboxylic acid side chains form crystalline hydrogen-bonding frameworks in the solid state. Depending on the length of the linker between the reactive sites and the malonate units, the distance of the [60]fullerene nodes and thereby the spacing of the frameworks can be controlled and for the most elongated derivative, continuous channels are obtained within the structure. Stability, structural integrity and porosity of the material were investigated by powder X-ray diffraction, thermogravimetry and sorption measurements.

Single crystals were mounted on a 100 µm MiTeGen MicroLoop using perfluorinated polyalkylether. Single crystal X-ray diffraction data were collected on a Bruker D8 Quest Kappa diffractometer with a Photon100 CMOS detector and multi-layered mirror monochromated CuK α radiation. The images were processed with the Bruker software packages and equivalent reflections were merged. The data were corrected for absorption effects using semi-empirical methods from equivalents. Corrections for Lorentz and polarization effects were applied. The structures were solved by direct methods, refined with the SHELXTL software package (G. Sheldrick, Acta Crystallogr. Sect. A, 2008, 64, 112) and expanded using Fourier techniques. All non-hydrogen atoms were refined anisotropically. Hydrogen atoms were assigned to geometrically idealized positions and were included in structure factor calculations.

Crystal data and refinement details for HFF-2:
Suitable crystals for X-ray diffraction have been obtained by slow vapor deposition of      Figure S12: Thermal behavior of crystalline HFF-3 under ambient conditions. S12

Electron microscopy (SEM)
Morphological investigations were determined on a field emission scanning electron microscope (FE-SEM) ULTRA plus (Zeiss) with a GEMINI e-beam column at 5 kV. Figure S13: SEM images of HFF-3 as-synthesized (top) and subsequent to activation (bottom) indicating the strong anisotropic crystal habitus, which does not change upon activation. S13

Sorption study (BET)
All sorption experiments were carried out on a Quantachrome Autosorb AS-1C. N 2 (Linde Gas, purity > 99.999%) and Ar (Linde Gas, purity > 99.999%) physisorption were determined at 77 K with dynamic p 0 -determination via a p0-cell at p = 760 mmHg. Analysis and interpretation of data were done with the Quantachrome AS1Win software package, version 2.11. HFF-3 samples were activated at room temperature and at 70 °C with pressures of 2.0 × 10 −3 mbar and 1 × 10 −6 mbar for 24 h, each. All samples were treated in the outgas station, until outgassing rates were at least below 2 microns/minute in pressure increase and afterwards loaded with He (Linde Gas, purity > 99.999%) before analysis was carried out. cm 3 /g desorption adsorption Figure S14: Adsorption and desorption isotherms of HFF-3 for N 2 (red) and Ar adsorption (black) at 77K.

Powder X-ray diffraction (PXRD)
Powder diffraction samples were either grinded and put into Lindemann glass capillaries (Ø 0.3 mm) for the as-synthesized product or investigated on a plate with dome sample holder for the activated samples. Diffraction data was collected on a BRUKER AXS D8 Discover powder X-ray diffractometer equipped with Lynx-Eye detector in transmission geometry (as-synthesized) and reflection geometry (activated). The X-ray radiation (Cu-Kα1; λ = 154.06 pm) was focused with a Goebel mirror, Cu-Kα2 radiation was eliminated by the application of a Ni absorber. Diffraction patterns were recorded and analysed using the program package BRUKER AXS Diffrac-Suite. pattern of HFF-3 as synthesized (red: measured without rotation, orange: measured without rotation) in comparison with a pattern simulated from single-crystal data (black). S15 Figure S16: Diffraction patterns of HFF-3 as-synthesized (red) in comparison with a pattern simulated with singly crystal data (black) and subsequent to activation treatment at 2 × 10 −3 mbar (blue) and 1 × 10 −6 mbar (pink).
low vacuum S16 6 TG/DTA study Figure S17: TG/DTA study for HFF-3 a) as synthesized and b) after activation at 70 °C under vacuum.