4.7 Article

Cobalt(II) Coordination Polymers Assembled from Unexplored Pyridine-Carboxylic Acids: Structural Diversity and Catalytic Oxidation of Alcohols

期刊

INORGANIC CHEMISTRY
卷 58, 期 9, 页码 5875-5885

出版社

AMER CHEMICAL SOC
DOI: 10.1021/acs.inorgchem.9b00242

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资金

  1. National Natural Science Foundation of China [21201091]
  2. Foundation for Science and Technology (FCT)
  3. Portugal 2020 [IF/01395/2013/CP1163/CT005, CEECIND/03708/2017, UID/QUI/00100/2013, IST-ID/086/2018, LISBOA-01-0145-FEDER-029697]
  4. RUDN University Program 5-100
  5. COST Action [CA15106]

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New coordination polymers of cobalt(II), namely, [Co(mu(4)-cpna)-(H2O)(2)](n) (1), [Co(mu(3)-cpna)(phen)(H2O)](n)center dot nH(2)O (2), [Co-3(mu(4)-dppa)(2)(H2O)(6)](n)center dot 2nH(2)O (3), and [Co-3(mu(5)-dppa)(2)(mu-4,4'-bipy)(H2O)(2)](n)center dot 4nH(2)O (4), have been generated under hydrothermal conditions from CoCl2 center dot 6H(2)O, two different multifunctional pyridine-carboxylic acids {H(2)cpna: 5-(4-carboxyphenoxy)nicotinic acid; H(3)dppa: 5-(3,4-dicarboxylphenyl)picolinic acid}, and optional N,N-supporting ligands {phen: 1,10-phenanthroline; 4,4'-bipy: 4,4'-bipyridine} acting as mediators of crystallization. These Co(II) coordination polymers (CPs) have been obtained as stable crystalline materials and characterized by conventional solid-state techniques, including X-ray crystallography. The obtained products are 3D metal-organic frameworks (MOFs 1 and 4) or 2D coordination polymers (CPs 2 and 3). Analysis of the topologies of simplified nets has revealed the sra (1), fes (2), and 3,4L13 (3) networks, in addition to a very complex topologically unique framework in 4. An observed diversity of structures is driven by types of carboxylate building blocks and crystallization mediators. Thermal stability and magnetic and catalytic properties of 1-4 have also been studied. In fact, the Co(II) compounds act as heterogeneous catalysts for the oxidation of alcohols with tBuOOH (tert-butylhydroperoxide) under mild conditions. Compound 2 features a good catalytic activity (up to 45% yield) in the oxidation of 1-indanol to 1-indanone. Finally, products 1-4 broaden a still very small number of CPs or MOFs driven by the present type of multifunctional pyridine-carboxylic acids (H(2)cpna, H(2)dppa).

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