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One plus two: supramolecular coordination in a nano-reactor on surface.

ABSTRACT: The supramolecular coordination of zinc (II) phthalocyanine (Zn-Pc) with V-shaped bi-pyridine in a nano-reactor is probed by scanning tunneling microscopy (STM) at liquid/solid interface. Combined with density functional theory (DFT) calculations, our STM results show that the V-shaped bi-pyridine and Zn-Pc can generate stable "odd-even" patterned architectures in the TCDB network through a two-step coordination process. Moreover, great changes for the size and the shape of the host cavity have happened during the coordination process. In general, the whole coordination process is regulated by the synergies of ligand and template. To the best of our knowledge, this is the first work on imaging of supramolecular coordination in a nano-reactor. Such a template-regulated supramolecular interconversion opens a new avenue towards the crystal engineering and design as well as the generation of controllable nano-patterns.

SUBMITTER: Zhang X

PROVIDER: S-EPMC3474287 | biostudies-literature | 2012

REPOSITORIES: biostudies-literature

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One plus two: supramolecular coordination in a nano-reactor on surface.

Zhang Xuemei X Shen Yongtao Y Wang Shuai S Guo Yuanyuan Y Deng Ke K Wang Chen C Zeng Qingdao Q

Scientific reports 20121017

The supramolecular coordination of zinc (II) phthalocyanine (Zn-Pc) with V-shaped bi-pyridine in a nano-reactor is probed by scanning tunneling microscopy (STM) at liquid/solid interface. Combined with density functional theory (DFT) calculations, our STM results show that the V-shaped bi-pyridine and Zn-Pc can generate stable "odd-even" patterned architectures in the TCDB network through a two-step coordination process. Moreover, great changes for the size and the shape of the host cavity have ...[more]

PMID: 23077726

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Project description:Silica materials attract an increasing amount of interest in (fundamental) research, and find applications in, for example, sensing, catalysis, and drug delivery. As the properties of these (nano)materials not only depend on their chemistry but also their size, shape, and surface area, the controllable synthesis of silica is essential for tailoring the materials to specific applications. Advantageously, bioinspired routes for silica production are environmentally friendly and straightforward since the formation process is spontaneous and proceeds under mild conditions. These strategies mostly employ amine-bearing phosphorylated (bio)polymers. In this work, we expand this principle to supramolecular polymers based on the water-soluble cationic cyanine dye Pinacyanol acetate. Upon assembly in water, these dye molecules form large, polyaminated, supramolecular fibers. The surfaces of these fibers can be used as a scaffold for the condensation of silicic acid. Control over the ionic strength, dye concentration, and silicic acid saturation yielded silica fibers with a diameter of 25?nm and a single, 4?nm pore. Unexpectedly, other unusual superstructures, namely, nummulites and spherulites, are also observed depending on the ionic strength and dye concentration. Transmission and scanning electron microscopy (TEM and SEM) showed that these superstructures are formed by aligned silica fibers. Close examination of the dye scaffold prior silicification using small-angle X-ray scattering (SAXS), and UV/Vis spectroscopy revealed minor influence of the ionic strength and dye concentration on the morphology of the supramolecular scaffold. Total internal reflection fluorescence (TIRF) during silicification unraveled that if the reaction is kept under static conditions, only silica fibers are obtained. Experiments performed on the dye scaffold and silica superstructures evidenced that the marked structural diversity originates from the arrangement of silica/dye fibers. Under these mild conditions, external force fields can profoundly influence the morphology of the produced silica.

Dataset Information

One plus two: supramolecular coordination in a nano-reactor on surface.

Publications

One plus two: supramolecular coordination in a nano-reactor on surface.

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