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Open AccessFeature PaperArticle

New Copper(II) Coordination Compounds Assembled from Multifunctional Pyridine-Carboxylate Blocks: Synthesis, Structures, and Catalytic Activity in Cycloalkane Oxidation

1
Foshan Research Center for Special Functional Building Materials and Their Green Preparation Technology, Guangdong Industry Polytechnic, Guangzhou 510300, China
2
College of chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000, China
3
Centro de Química Estrutural, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049-001 Lisbon, Portugal
4
Peoples’ Friendship University of Russia (RUDN University), Research Institute of Chemistry, 6 Miklukho-Maklaya st., Moscow 117198, Russia
*
Authors to whom correspondence should be addressed.
Academic Editors: Luís Cunha Silva and Filipe Alexandre Almeida Paz
Molecules 2019, 24(1), 6; https://doi.org/10.3390/molecules24010006
Received: 25 November 2018 / Revised: 15 December 2018 / Accepted: 18 December 2018 / Published: 20 December 2018
(This article belongs to the Special Issue Functional Metal-Organic Framework Based Materials)
Two new copper(II) coordination compounds, namely a 1D coordination polymer [Cu(µ-cpna)(phen)(H2O)]n (1) and a discrete tetracopper(II) derivative [Cu(phen)2(H2O)]2[Cu2(µ-Hdppa)2(Hdppa)2] (2), were hydrothermally synthesized from copper(II) chloride as a metal source, 5-(4-carboxyphenoxy)nicotinic acid (H2cpna) or 5-(3,4-dicarboxylphenyl)picolinic acid (H3dppa) as a principal building block, and 1,10-phenanthroline (phen) as a crystallization mediator. Compounds 1 and 2 were isolated as air-stable microcrystalline solids and fully characterized by elemental and thermogravimetric analyses, IR spectroscopy, powder and single-crystal X-ray diffraction. In the solid state, the structure of 1 discloses the linear interdigitated 1D coordination polymer chains with the 2C1 topology. The crystal structure of an ionic derivative 2 shows that the mono- and dicopper(II) units are extended into the intricate 1D hydrogen-bonded chains with the SP 1-periodic net (4,4)(0,2) topology. Thermal stability and catalytic properties of 1 and 2 were also investigated. In fact, both Cu derivatives act as efficient homogeneous catalysts (catalyst precursors) for the mild oxidation of cycloalkanes by hydrogen peroxide to give the corresponding alcohols and ketones; the substrate scope and the effects of type and amount of acid promoter as well as bond-, regio-, and stereo-selectivity features were investigated. View Full-Text
Keywords: hydrothermal synthesis; crystal structure; coordination polymers; self-assembly; catalysis; alkanes; cyclohexane; oxidation reactions; hydrogen peroxide hydrothermal synthesis; crystal structure; coordination polymers; self-assembly; catalysis; alkanes; cyclohexane; oxidation reactions; hydrogen peroxide
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MDPI and ACS Style

Zhao, N.; Li, Y.; Gu, J.; Fernandes, T.A.; Kirillova, M.V.; Kirillov, A.M. New Copper(II) Coordination Compounds Assembled from Multifunctional Pyridine-Carboxylate Blocks: Synthesis, Structures, and Catalytic Activity in Cycloalkane Oxidation. Molecules 2019, 24, 6.

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