Ad irected heterogeneousC ÀHa ctivation/halogenation reaction catalyzed by readily synthesized Pd@MOF nanocatalysts was developed. The heterogeneous Pd catalysts used were an ovel and environmentally benign Febased metal-organic framework (MOF) (Pd@MIL-88B-NH 2 (Fe)) and the previously developed Pd@MIL-101-NH 2 (Cr). Very high conversionsa nd selectivities were achieved under very mild reactionc onditions and in short reactiont imes. A wide variety of directing groups, halogen sources,a nd substitutionpatterns were well tolerated, and valuablepolyhalogenated compounds were synthesized in ac ontrolled manner.T he synthesis of the Pd-functionalized Fe-based MOF and the recyclability of the two catalysts are also presented.

An electron donor-acceptor dyad based on a polychlorotriphenylmethyl (PTM) radical subunit linked to a tetrathiafulvalene (TTF) unit through a π-conjugated N-phenyl-pyrrole-vinylene bridge has been synthesized and characterized. The intramolecular electron transfer process and magnetic properties of the radical dyad have been evaluated by cyclic voltammetry, UV/Vis spectroscopy, vibrational spectroscopy, and ESR spectroscopy in solution and in the solid state. The self-assembling abilities of the radical dyad and of its protonated non-radical analogue have been investigated by X-ray crystallographic analysis, which revealed that the radical dyad produced a supramolecular architecture with segregated donor and acceptor units in which the TTF subunits were arranged in 1D herringbone-type stacks. Analysis of the X-ray data at different temperatures suggests that the two inequivalent molecules that form the asymmetric unit of the crystal of the radical dyad evolve into an opposite degree of electronic delocalization as the temperature decreases.

SummaryThe electron-donor and unique redox properties of the tetrathiafulvalene (TTF, 1) moiety have led to diverse applications in many areas of chemistry. Monopyrrolotetrathiafulvalenes (MPTTFs, 4) and bispyrrolotetrathiafulvalenes (BPTTFs, 5) are useful structural motifs and have found widespread use in fields such as supramolecular chemistry and molecular electronics. Protocols enabling the synthesis of functionalised MPTTFs and BPTTFs are therefore of broad interest. Herein, we present the synthesis of a range of functionalised MPTTF and BPTTF species. Firstly, the large-scale preparation of the precursor species N-tosyl-(1,3)-dithiolo[4,5-c]pyrrole-2-one (6) is described, as well as the synthesis of the analogue N-tosyl-4,6-dimethyl-(1,3)-dithiolo[4,5-c]pyrrole-2-one (7). Thereafter, we show how 6 and 7 can be used to prepare BPTTFs using homocoupling reactions and functionalised MPTTFs using cross-coupling reactions with a variety of 1,3-dithiole-2-thiones (19). Subsequently, the incorporation of more complex functionality is discussed. We show how the 2-cyanoethyl protecting group can be used to afford MPTTFs functionalised with thioethers, exemplified by a series of ethylene glycol derivatives. Additionally, the merits of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) as an alternative to the most common deprotecting agent, CsOH·H2O are discussed. Finally, we show how a copper-mediated Ullman-type reaction can be applied to the N-arylation of MPTTFs and BPTTFs using a variety of aryl halides.

Three new hybrid gated mesoporous materials (SN3 -1, SNH2 -2, and SN3 -3) loaded with the dye [Ru(bipy)3 ](2+) (bipy=bipyridine) and capped with different tetrathiafulvalene (TTF) derivatives (having different sizes and shapes and incorporating different numbers of sulfur atoms) have been prepared. The materials SN3 -1 and SN3 -3 are functionalized on their external surfaces with the TTF derivatives 1 and 3, respectively, which were attached by employing the "click" chemistry reaction, whereas SNH2 -2 incorporates the TTF derivative 2, which was anchored to the solid through an amidation reaction. The final gated materials have been characterized by standard techniques. Suspensions of these solids in acetonitrile showed "zero release", most likely because of the formation of dense TTF networks around the pore outlets. The release of the entrapped [Ru(bipy)3 ](2+) dye from SN3 -1, SNH2 -2, and SN3 -3 was studied in the presence of selected explosives (Tetryl, TNT, TNB, DNT, RDX, PETN, PA, and TATP). SNH2 -2 showed a fairly selective response to Tetryl, whereas for SN3 -1 and SN3 -3 dye release was found to occur with Tetryl, TNT, and TNB. The uncapping process in the three materials can be ascribed to the formation of charge-transfer complexes between the electron-donating TTF units and the electron-accepting nitroaromatic explosives. Finally, solids SNH2 -2 and SN3 -1 have been tested for Tetryl detection in soil with good results, pointing toward a possible use of these or similar hybrid capped materials as probes for the selective chromo-fluorogenic detection of nitroaromatic explosives.

Herein, we report a versatile carbonylation protocol using heterogeneous Pd0 nanoparticles supported on the metal–organic frameworks (MOFs) MIL‐88B‐NH2 (Fe/Cr). The synthesis of a vast array of carbonyls, which includes amides, esters, carboxylic acids, and α‐ketoamides, was achieved through mono‐ and dicarbonylation reactions. The selectivity could be controlled simply by tuning the reaction conditions. Superior activity and selectivity were recorded in some cases compared to that achieved with commercial Pd/C. However, the utility of an elaborate catalyst support is questionable and important reactivity and recyclability issues are discussed.