This template will self-destruct: A unique particle-growth mechanism involves growth of new coordination polymers on the surface of initially formed hexagonal blocks and concomitant dissolution of the blocks to form hexagonal tubes (see scheme and scanning electron, optical, and fluorescence microscopy images). Calcination of the tubes yields ZnO particles of the same shape.
Infinite coordination polymers in which metal ions or metal clusters are connected by molecular building blocks consisting of organic molecules or organometallic complexes have received a great deal of attention due to their useful applications in gas storage, [1] catalysis, [2] optics, [3] recognition, and separation.[4] Rationalization of their chemical and physical properties from structural studies is of fundamental interest in the field of coordination polymer materials. Similarly, micro-and nanostructured materials are essential in many different areas, such as catalysis, [5] optics, [6] biosensing, [7] medical diagnostics, [8] and data storage, [9] and their size, shape, and composition are the key parameters that dictate chemical and physical properties.[10] Recently, a synthetic strategy for the preparation of micro-and nanoparticles made from infinite coordination polymers has been demonstrated by several groups.[11] This new class of materials promises to advance nanoparticle science into the realm of infinite coordination polymers, and thereby circumvent the nominal composition limitations generally ascribed to nanoparticles.Control of the composition of nanoparticles generated from functionally defined precursors is a promising research area due to the fundamental interest in materials that have practical applications in chemistry, biology, physics, and related interdisciplinary fields. Coordination polymer particles (CPPs) made from functional metalloligand building blocks have been shown to have a high degree of tailorability.[11a, b] The development and application of CPP materials requires an understanding of how the particles are formed, and the ability to control their size and shape. Herein we describe a solvothermal approach for the synthesis of CPPs made from transition-metal ions and metallosalen (salen = N,N'-bis(salicylidene)ethylenediamine) building blocks. We also describe an interesting nanoparticle wire-to-cube morphological transformation, and the utilization of this transformation process to control CPP formation.In a typical synthesis, fluorescent cubic nanoparticles were prepared by the following simple procedure (Scheme 1):carboxy-functionalized salen ligand N,N'-phenylenebis(salicylideneimine)dicarboxylic acid [12a] (1, 3 mg) was dissolved in DMSO (1 mL), and the solution was added to DMF (2 mL) containing two equivalents Zn(OAc) 2 . One equivalent of Zn 2+ coordinates to the salen pocket to give Zn-metalated salen (Zn-MS) [12] complex. The other Zn 2+ ion acts as a node that connects to the Zn-MS metalloligands through the carboxylate groups to form coordination polymer (Zn-MSZn); when one equivalent Zn 2+ is used, the coordination polymer does not form. The resulting solution was heated at 120 8C for 60 min. During this time, formation of particles was observed. The reaction mixture was cooled to room temperature, and the precipitate was collected by centrifugation and washed several times with DMSO and methanol. The resulting particles were found to be stable in organic so...
Dielectrophoresis has received considerable attention for separating nanotubes according to electronic types. Here we examine the effects of surface conductivity of semiconducting single walled carbon nanotubes (SWNT), induced by ionic surfactants, on the sign of dielectrophoretic force. The crossover frequency of semiconducting SWNT increases rapidly as the conductivity ratio between the particle and medium increases, leading to an incomplete separation of ionic surfactant suspended SWNT at an electric field frequency of 10 MHz. To reduce the conductivity ratio, the surface charge of SWNT is neutralized by an equimolar mixture of anionic surfactant sodium dodecyl sulfate (SDS) and cationic surfactant cetyltrimethylammonium bromide (CTAB), resulting in negative dielectrophoresis of semiconducting species at 10 MHz. A comparative Raman spectroscopy study shows a nearly complete separation of metallic SWNT.
Multi-valued logic gates are demonstrated on solution-processed molybdenum disulfide (MoS2) thin films. A simple chemical doping process is added to the conventional transistor fabrication procedure to locally increase the work function of MoS2 by decreasing sulfur vacancies. The resulting device exhibits pseudo-heterojunctions comprising as-processed MoS2 and chemically treated MoS2 (c-MoS2). The energy-band misalignment of MoS2 and c-MoS2 results in a sequential activation of the MoS2 and c-MoS2 channel areas under a gate voltage sweep, which generates a stable intermediate state for ternary operation. Current levels and turn-on voltages for each state can be tuned by modulating the device geometries, including the channel thickness and length. The optimized ternary transistors are incorporated to demonstrate various ternary logic gates, including the inverter, NMIN, and NMAX gates.
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