Eduardo H. L. Falcao

Enhanced H2 adsorption enthalpy in the low-surface area, partially fluorinated coordination polymer Zn5(triazole)6(tetrafluoroterephthalate)2(H2O)2·4H2O

A porous coordination polymer containing zinc, 1,2,4-triazolate, and tetrafluoroterephthalate displays a high physisorptive hydrogen adsorption enthalpy of 8 kJ/mol, as a result of fluorine atoms exposed to the pore surface and the structures small pore size.

Hybrid organic-inorganic framework structures: influence of cation size on metal-oxygen-metal connectivity in the alkaline earth thiazolothiazoledicarboxylates.

We report the synthesis of four organic-inorganic frameworks of alkaline earth cations with the organic ligand 2,5-thiazolo[5,4-d]thiazoledicarboxylate (C6N2S2O4(2-), Thz(2-)). Structures with remarkably different connectivities result when Mg(2+), Ca(2+), Sr(2+), and Ba(2+) react with Thz(2-). Mg(Thz)(H2O)4 (I) forms a 1-D coordination polymer in which one carboxylate oxygen on each terminus of the ligand connects individual MgO6 octahedra from their axial positions, while the remaining equatorial sites are coordinated by water molecules. Ca2(Thz)2(H2O)8 (II) forms a 1-D coordination polymer in which dimeric clusters with 7-fold Ca coordination are connected via the ligand in a linear fashion, with a second, uncoordinated Thz(2-) providing charge balance. Sr(Thz)(H2O)3 (III) has 1-D infinite inorganic connectivity built from edge-sharing SrO7N polyhedra having one carboxylate oxygen and one water molecule acting as M-O-M bridges. Ba2(Thz)2(H2O)7 (IV) has 2-D inorganic connectivity based upon face- and edge-sharing BaO9N polyhedra. One carboxylate oxygen and all water molecules act as bridges between each Ba(2+) and its three neighbors. We shall discuss the manner in which the increasing coordination requirements of the cations (MgO6 < CaO7 < SrO7N < BaO9N) lead to an increase in inorganic connectivity through the series.

Organic single-crystal complementary inverter

The authors demonstrate the operation of an organic single-crystal complementary circuit in the form of a simple inverter. The device is constructed from a high mobility p-type organic single-crystal transistor of tetramethylpentacene (TMPC) and a n-type single-crystal transistor of N,N′-di[2,4-difluorophenyl]-3,4,9,10-perylenetetracarboxylic diimide (PTCDI). Field-effect mobilities of up to 1.0cm2∕Vs are reported for TMPC devices, while a mobility of 0.006cm2∕Vs is reported for a n-type PTCDI single-crystal device. Considering that organic single-crystal inverters have not yet been explored, they are representative of potential candidates for use in high-performance complementary circuits.

Temperature-induced water release and uptake in organic porous networks.

The behavior of water confined near nonpolar surfaces has important implications for a number of biological phenomena. In this type of confined environment the properties of hydrophobicity and hydrophilicity are closely related to the structure of the interfacial water, which in turn can depend on temperature in a very subtle way. Although the physical-chemical consequences of this fact have been theoretically addressed to a great extent, the underlying thermodynamic question is still widely discussed. Accordingly we performed thermogravimetric analysis and variable-temperature powder X-ray diffraction studies on representative hydrogen bonding organic pores occupied by water. The results indicate that a hydrophilic-to-hydrophobic transition of the inner surface of the pores occurs upon increasing temperature, which may be attributed to a strong influence of the dynamics and thermodynamics of local water molecules on the surface affinity of the pores. The relevance of our findings to the understanding of the phenomenon of water transport in natural pores is discussed.