. (2012). Large scale synthesis of V-shaped rutile twinned nanorods. CrystEngComm, 14 (9), 3120-3124.Large scale synthesis of V-shaped rutile twinned nanorods Abstract V-shaped rutile twinned nanorods (VRTNs) with different aspect ratios were synthesized on large scale using a one-pot organic solvothermal method. Although several different types of VRTNs were produced, (101) twinned nanorods were the major product with minor amounts of (301) twins and straight nanorods. STEM, TEM and XRD characterizations show that [001] is the growth direction of VRTNs, with surfaces dominated by {110} facets. Intermediate formation of both brookite and anatase nanorods provides dual pathways to VRTNs' growth: one path in which anatase seeds trigger and promote brookite nanorod growth; and a second path in which anatase nanorods are formed by oriented attachment. Subsequent dissolution of both brookite and anatase nanorods provides titania to support VRTNs growth. V-shaped rutile twinned nanorods (VRTNs) with different aspect ratios were synthesized on large scale using a one-pot organic solvothermal method. Although several different types of VRTNs were produced, (101) twinned nanorods were the major product with minor amounts of (301)
The complex [Ru(bpy)2(ttma)](+) (bpy = 2,2'-bipyridine; ttma = 3-hydroxy-2-methyl-thiopyran-4-thionate, 1, has previously been shown to undergo an unusual C-H activation of the dithiomaltolato ligand upon outer-sphere oxidation. The reaction generated alcohol and aldehyde products 2 and 3 from C-H oxidation of the pendant methyl group. In this report, we demonstrate that the same products are formed upon photolysis of 1 in presence of mild oxidants such as methyl viologen, [Ru(NH3)6](3+) and [Co(NH3)5Cl](2+), which do not oxidize 1 in the dark. This reactivity is engendered only upon excitation into an absorption band attributed to the ttma ligand. Analogous experiments with the homoleptic Zn(ttma)2, 4, also result in reduction of electron acceptors upon excitation of the ttma absorption band. Complexes 1 and 4 exhibit short-lived visible fluorescence and long-lived near-infrared phosphorescence bands. Singlet oxygen is both generated and quenched during aerobic excitation of 1 or 4, but is not involved in the C-H activation process.
Recently, rutile nanotwins were synthesized using high temperature organic solvent methods, yielding two kinds of common high-quality rutile twinned nanocrystals, (101) and (301) twins, accompanied by minor rutile nanorods (Lu et al 2012 CrystEngComm 14 3120-4). In this report, the atomic structures of the rutile and anatase nanocrystals are directly resolved with no need for calculation or image simulation using atomic resolution STEM techniques. The locations of the oxygen rows in the rutile twins' boundaries are directly determined from both HAADF images and ABF images. To the best of our knowledge, this is the first time oxygen columns have been distinguished in rutile twin boundaries using HAADF and BF imaging.
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