☆ 4.6 Article

Pyrazino[2.3-g]quinoxaline-Bridged Indole-Based Building Blocks: Design, Synthesis, Anion-Binding Properties, and Phosphate-Directed Assembly in the Solid State

CHEMISTRY-A EUROPEAN JOURNAL (2010)

Journal

CHEMISTRY-A EUROPEAN JOURNAL

Volume 16, Issue 15, Pages 4639-4649

Publisher

WILEY-V C H VERLAG GMBH

DOI: 10.1002/chem.200903188

Keywords

anions; chain structures; crystal engineering; self-assembly; supramolecular chemistry

Funding

National Natural Science Foundation of China [20935001]
National Basic Research Program of China [2006CB705703]

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Abstract

Strategies for exploring anionic templates to direct sophisticated supramolecular assembly have attracted attention. Herein, a series of new anion receptors 1-3 containing two indole-based binding sites bridged by linking spacer pyrazino[2.3-g]quinoxaline (PQ) have been rationally designed and prepared from the precursors 2,3-diindo1-3'-yl quinoxaline (DIQ) and 5,6-dihydrodiindolo[3,2-a:2',3'-c]-phenazine (DIPZ). X-ray analyses showed a self-connected network and dimeric packing through hydrogen bonding and pi-pi stacking interaction M the solid state in the structures of 1 and 2, respectively. All three receptors exhibited a series of prominent absorption bands from the expanded pi system. The indole-based expanded receptors were found to strongly and selectively bind F-, AcO-, and H2PO4- among the tested anions (F-, Cl-, Br-, AcO-, H2PO4-, HSO4-. NO3-, and ClO4-), and operated as efficient colorimetric sensors for naked-eve detection of fluoride anions in DMSO. These tailored building blocks captured two anions located at far-spaced binding sites, and adopted noninterfering anion-binding processes to guarantee the anion-binding affinity, topology, and dimensionality. Solid-state studies elucidated that the neutral 1-3 interacted with the tetrahedral dihydrogen phosphate anion in proper proportions and designed topologies, thus leading to the formation of a series of multidimensional networks by self-assembly in the solid state. The observations showed a well-characterized phosphate-directed assembly of multidimensional metal-free coordination polymers in the solid state, in which the formed phosphate aggregates. including dimer encapsulated in an indole-mediated hydrogen-bonded pocket and an infinite chain, behaved as anionic templates to direct the self-assembly. However. no evidence proved the presence of such phosphate-directed infinite coordination polymers in solution.

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Intermolecular Halogen and Hydrogen Bonding-Controlled Self-Assembly of Network Structures

Li Fen, Liu Chuanzhi, Hu Zhiyuan, Luo Panpan, Cui Rongzheng, Huang Yanke, Liu Xinming, Liu Lantao, Wu Wei

Summary: Two types of tetra-dentate halogen bonding donors were synthesized using tetrafluoroiodide benzene in tetraphenylene methane and tetraphenyl porphyrin modules. 3,3',5,5'-Tetramethyl-4,4'-bipyridine (TMBP) was used as a halogen bonding acceptor. Through self-assembly, a supramolecular network structure was formed in the solid phase based on intermolecular I···N halogen bonds and H···N hydrogen bonds. Crystal structure revealed the binding patterns of the molecules and the stacking controlled by other hydrogen and halogen bonds.

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