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Solvothermal reactions of the flexible, pyrazole-based 1,4-bis((3,5-dimethyl-1H-pyrazol-4-yl)methyl)benzene ligand (H(2)BDMPX) with late transition metal ions allowed the isolation of the four coordination compounds M(x)(BDMPX) (x = 1 for M = Zn, 1; Co, 2; Cd, 3; x = 2 for M = Cu, 4). The investigation of the thermal behavior assessed the high thermal robustness of these materials, which are stable in air at least up to 300 °C, with the Cd(II) derivative starting to decompose only around 500 °C. As retrieved by ab initio X-ray powder diffraction, the isomorphous compounds 1-3 possess a dense 3-D network featuring rhombic motifs hinged about rigid and parallel chains of tetrahedral MN(4) chromophores. As demonstrated by thermodiffractometric measurements, temperature increase triggers framework flexibility. The latter is at work also when N(2) adsorption is assayed at 77 K: 1 and 2 show permanent porosity, with BET and Langmuir specific surface areas of 515, 667 m(2)/g and 209, 384 m(2)/g, respectively. 1 and 2 thus represent an intriguing example of "porosity without pores", their pro-porous nature being explained in terms of the flexibility of the rhombic motifs, stimulated by the gas probe and facilitated by the nature of the ligand.

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We report here on soft-template electropolymerizations of polypyrrole (Ppy)-based nanocomposites triggered by graphene platelets (GP) from shungite (SH) rocks. A properly designed procedure for an efficient extraction of graphene platelets from SH powders is established to produce remarkable graphene materials in a low oxidation state and with a high electrical conductivity (1490 S cm−1). By using positively and negatively charged templating surfactants the role played by the graphene units on the electropolymerization reactions is pointed out by SEM, EDX, TEM, SAED, XPS and Raman spectroscopy. The morphological/structural characterizations highlight that GP from SH have a surface chemistry suitable for selective and mutual interactions with the growing Ppy chains. CV and galvanostatic charge/discharge measurements evidence that GP improve the transport of both electrons and ions within the bulk material by means of a synergistic action with the polymer phase. This cooperative behavior induces an enhancement of the specific capacitance up to 250 F g−1 at 2 A g−1. The Ppy-GP materials produced following the settled protocols result to be appropriate for fabricating multifunctional charge transport and storage electroactive systems.