We describe a versatile and scalable strategy toward long-range and periodically ordered mesoporous alumina (Al 2 O 3 ) structures by evaporationinduced self-assembly of a structure-directing ABA triblock copolymer (F127) mixed with aluminum tri-sec-butoxide-derived sol additive. We found that the separate preparation of the alkoxide sol−gel reaction before mixing with the block copolymer enabled access to a relatively unexplored parameter space of copolymerto-additive composition, acid-to-metal molar ratio, and solvent, yielding ordered mesophases of two-dimensional (2D) lamellar, hexagonal cylinder, and 3D cage-like cubic lattices, as well as multiscale hierarchical ordered structures from spinodal decomposition-induced macro-and mesophase separation. Thermal annealing in air at 900 °C yielded well-ordered mesoporous crystalline γ-Al 2 O 3 structures and hierarchically porous γ-Al 2 O 3 with 3D interconnected macroscale and ordered mesoscale pore networks. The ordered Al 2 O 3 structures exhibited tunable pore sizes in three different length scales, <2 nm (micropore), 2−11 nm (mesopore), and 1−5 μm (macropore), as well as high surface areas and pore volumes of up to 305 m 2 /g and 0.33 cm 3 /g, respectively. Moreover, the resultant mesoporous Al 2 O 3 demonstrated enhanced adsorption capacities of carbon dioxide and Congo red dye. Such hierarchically ordered mesoporous Al 2 O 3 are well-suited for green environmental solutions and urban sustainability applications, for example, hightemperature solid adsorbents and catalyst supports for carbon dioxide sequestration, fuel cells, and wastewater separation treatments.

A variety of new and known transition metal dithiolene complexes has been synthesized from thiometalates via induced internal electron-transfer reactions. Treating MS4 2- (M = Mo, W) with stoichiometric amounts of bis(trifluoromethyl)-1,2-dithiete ((CF3)2C2S2) results in rapid formation of the respective tris(dithiolene) complexes M(tfd)3 2- (tfd = [(CF3)2C2S2]2-). These complexes are isostructural and adopt twisted trigonal prismatic coordination (ca. 18° from a perfect trigonal prism). Crystal data:  Mo(tfd)3 2-, monoclinic, space group C2/c, with a = 18.905(4) Å, b = 13.732(3) Å, c = 17.101(3) Å, β = 110.29(3)°, and Z = 4; W(tfd)3 2-, monoclinic, space group C2/c, with a = 18.933(4) Å, b = 13.728(3) Å, c = 17.096(3) Å, β = 110.26(3)°, and Z = 4. In contrast, Mo(tfd)3 (synthesized as reported previously) has nearly perfect trigonal prismatic coordination. Crystal data:  hexagonal, space group P63/m, with a = 9.6795(14) Å, b = 9.6795(14) Å, c = 13.951(3) Å, and Z = 2. Treating WOS3 2- and MoO2S2 2- with (CF3)2C2S2 results in the respective MO(tfd)2 2- complexes. These two complexes are isostructural and adopt square pyramidal coordination with four sulfur atoms forming the base and oxygen at the apex. Crystal data:  MoO(tfd)2 2-, monoclinic, space group P21/n, with a = 12.184(2) Å, b = 18.627(4) Å, c = 15.482(3) Å, β = 91.06(3)°, and Z = 4; WO(tfd)2 2-, monoclinic, space group P21/n, with a = 12.200(2) Å, b = 18.630(4) Å, c = 15.463(3) Å, β = 91.02(3)°, and Z = 4. On the basis of spectroscopic evidence, the product from the reaction of ReS4 - with (CF3)2C2S2 is proposed to be {Re[S2C2(CF3)2][S3C2(CF3)2]2}-. Influences of the nature of the oxidant on the ease with which thiometalates undergo induced internal electron-transfer reactions are discussed.

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The chemistry of oxometalates and thiometalates was initiated at almost the same time in the early nineteenth century by Berzelius, who synthesized what turned out to be the [PMo^O^]3-1 and [M0S4]2-2 anions. Since then, research in oxometalates has progressed steadily,3,4 owing to their remarkable, accessible structural chemistry. Some of these compounds show potential in catalysis6,6 and in medicine.7 The corresponding chemistry of thiometalates has received serious attention Mohammad A. Ansari received his B.Sc. and M.Sc. degrees from Aligarh Muslim University, India. He completed his Ph.D. degree in 1988 at the