skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Metal-organic and supramolecular networks driven by 5-chloronicotinic acid: Hydrothermal self-assembly synthesis, structural diversity, luminescent and magnetic properties

Abstract

Four new crystalline solids, namely [Co{sub 2}(µ{sub 2}-5-Clnic){sub 2}(µ{sub 3}-5-Clnic){sub 2}(µ{sub 2}-H{sub 2}O)]{sub n} (1), [Co(5-Clnic){sub 2}(H{sub 2}O){sub 4}]·2(5-ClnicH) (2), [Pb(µ{sub 2}-5-Clnic){sub 2}(phen)]{sub n} (3), and [Cd(5-Clnic){sub 2}(phen){sub 2}]·3H{sub 2}O (4) were generated by hydrothermal self-assembly methods from the corresponding metal(II) chlorides, 5-chloronicotinic acid (5-ClnicH) as a principal building block, and 1,10-phenanthroline (phen) as an ancillary ligand (optional). All the products 1–4 were characterized by IR spectroscopy, elemental analysis, thermogravimetric (TGA), powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. Their structures range from an intricate 3D metal-organic network 1 with the 3,6T7 topology to a ladder-like 1D coordination polymer 3 with the 2C1 topology, whereas compounds 2 and 4 are the discrete 0D monomers. The structures of 2 and 4 are further extended (0D→2D or 0D→3D) by hydrogen bonds, generating supramolecular networks with the 3,8L18 and ins topologies, respectively. Synthetic aspects, structural features, thermal stability, magnetic (for 1) and luminescent (for 3 and 4) properties were also investigated and discussed. - Graphical abstract: A new series of crystalline solids was self-assembled and fully characterized; their structural, topological, luminescent and magnetic features were investigated. Display Omitted.

Authors:
 [1];  [1];  [2];  [1];  [3]
  1. School of Chemical and Biological Engineering, Taiyuan University of Science and Technology, Taiyuan 030021 (China)
  2. College of Chemistry and Chemical Engineering, Lanzhou University, Lanzhou 730000 (China)
  3. Centro de Química Estrutural, Complexo I, Instituto Superior Técnico, Universidade de Lisboa, Av. Rovisco Pais, 1049–001 Lisbon (Portugal)
Publication Date:
OSTI Identifier:
22584202
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 241; Other Information: Copyright (c) 2016 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CARBON DIOXIDE; CHLORIDES; HYDROGEN; HYDROTHERMAL SYNTHESIS; INFRARED SPECTRA; LIGANDS; MAGNETIC PROPERTIES; MAGNETISM; MONOCRYSTALS; MONOMERS; PHENANTHROLINES; PHOTOLUMINESCENCE; POLYMERS; POWDERS; SOLIDS; STABILITY; THERMAL GRAVIMETRIC ANALYSIS; X RADIATION; X-RAY DIFFRACTION

Citation Formats

Gao, Zhu-Qing, E-mail: zqgao2008@163.com, Li, Hong-Jin, Gu, Jin-Zhong, E-mail: gujzh@lzu.edu.cn, Zhang, Qing-Hua, and Kirillov, Alexander M.. Metal-organic and supramolecular networks driven by 5-chloronicotinic acid: Hydrothermal self-assembly synthesis, structural diversity, luminescent and magnetic properties. United States: N. p., 2016. Web. doi:10.1016/J.JSSC.2016.05.034.
Gao, Zhu-Qing, E-mail: zqgao2008@163.com, Li, Hong-Jin, Gu, Jin-Zhong, E-mail: gujzh@lzu.edu.cn, Zhang, Qing-Hua, & Kirillov, Alexander M.. Metal-organic and supramolecular networks driven by 5-chloronicotinic acid: Hydrothermal self-assembly synthesis, structural diversity, luminescent and magnetic properties. United States. doi:10.1016/J.JSSC.2016.05.034.
Gao, Zhu-Qing, E-mail: zqgao2008@163.com, Li, Hong-Jin, Gu, Jin-Zhong, E-mail: gujzh@lzu.edu.cn, Zhang, Qing-Hua, and Kirillov, Alexander M.. 2016. "Metal-organic and supramolecular networks driven by 5-chloronicotinic acid: Hydrothermal self-assembly synthesis, structural diversity, luminescent and magnetic properties". United States. doi:10.1016/J.JSSC.2016.05.034.
@article{osti_22584202,
title = {Metal-organic and supramolecular networks driven by 5-chloronicotinic acid: Hydrothermal self-assembly synthesis, structural diversity, luminescent and magnetic properties},
author = {Gao, Zhu-Qing, E-mail: zqgao2008@163.com and Li, Hong-Jin and Gu, Jin-Zhong, E-mail: gujzh@lzu.edu.cn and Zhang, Qing-Hua and Kirillov, Alexander M.},
abstractNote = {Four new crystalline solids, namely [Co{sub 2}(µ{sub 2}-5-Clnic){sub 2}(µ{sub 3}-5-Clnic){sub 2}(µ{sub 2}-H{sub 2}O)]{sub n} (1), [Co(5-Clnic){sub 2}(H{sub 2}O){sub 4}]·2(5-ClnicH) (2), [Pb(µ{sub 2}-5-Clnic){sub 2}(phen)]{sub n} (3), and [Cd(5-Clnic){sub 2}(phen){sub 2}]·3H{sub 2}O (4) were generated by hydrothermal self-assembly methods from the corresponding metal(II) chlorides, 5-chloronicotinic acid (5-ClnicH) as a principal building block, and 1,10-phenanthroline (phen) as an ancillary ligand (optional). All the products 1–4 were characterized by IR spectroscopy, elemental analysis, thermogravimetric (TGA), powder X-ray diffraction (PXRD) and single-crystal X-ray diffraction. Their structures range from an intricate 3D metal-organic network 1 with the 3,6T7 topology to a ladder-like 1D coordination polymer 3 with the 2C1 topology, whereas compounds 2 and 4 are the discrete 0D monomers. The structures of 2 and 4 are further extended (0D→2D or 0D→3D) by hydrogen bonds, generating supramolecular networks with the 3,8L18 and ins topologies, respectively. Synthetic aspects, structural features, thermal stability, magnetic (for 1) and luminescent (for 3 and 4) properties were also investigated and discussed. - Graphical abstract: A new series of crystalline solids was self-assembled and fully characterized; their structural, topological, luminescent and magnetic features were investigated. Display Omitted.},
doi = {10.1016/J.JSSC.2016.05.034},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 241,
place = {United States},
year = 2016,
month = 9
}
  • Two novel 3D lanthanide metal-organic frameworks [Ln(pydc)(pip){sub 1/2}(H{sub 2}O] (Ln=Ce (1) and Pr (2), H{sub 2}pydc=2,5-pyridinedicarboxylic acid, H{sub 2}pip=2,5-piperazinedicarboxylic acid have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), powder X-ray diffractions (PXRD), and single-crystal X-ray diffractions. Field emission scanning electron microscopy (FESEM) was used for morphological analysis. Complexes are isostructural and feature interesting 3D frameworks. Both compounds crystallize in the monoclinic system, space group P2{sub 1}/c. Structural analyses of 1 and 2 show that Ln{sup 3+} ions connect with each other through H{sub 2}pydc and H{sub 2}pip. To the best of ourmore » knowledge, they are the first heteroleptic lanthanide polymers obtained through in situ 2,5-piperazinedicarboxylic acid syntheses. Moreover, thermal and luminescent properties of the compounds have been investigated. - Graphical abstract: Two novel 3D lanthanide metal-organic frameworks have been synthesized under hydrothermal conditions. Luminescent properties of the compounds in different temperatures have been also investigated. - Highlights: • New cerium and praseodymium coordination polymers based on N-O-bifunctional ligands have been synthesized In situ hydrothermal decarboxylation. • 2,5-pyridinedicarboxylic acid and piperazine were used as ligands. • In situ hydrothermal decarboxylation and formation of ligands were observed.« less
  • Graphical abstract: Monophasic and highly crystalline Self-dopant LaMnO{sub 3+δ} nanoparticles (72 nm) have been successfully synthesized at low temperature (773 K) by metal citrate complex method based on Pechini-type reaction route which showed ferromagnetic interaction. Surface areas of LaMnO{sub 3+δ} nanoparticles were found to be 157.4 and 153 m{sup 2} g{sup −1} for the samples annealed at 773 K and 1173 K, respectively. - Highlights: • Self-dopant LaMnO{sub 3+δ} nanoparticles using Pechini-type reaction route at 773 K. • Size range varies from 72 to 80 nm. • Surface area varies from 153 to 157 m{sup 2} g{sup −1}. • Extensivemore » characterization using sophisticated techniques. - Abstract: Self-dopant LaMnO{sub 3+δ} nanoparticles have been successfully synthesized by metal citrate complex method based on Pechini-type reaction route, at low temperature (773 K). Powder X-ray diffraction and transmission electron microscope revealed pure and nanostructured phase of LaMnO{sub 3+δ} (δ = 0.125) with an average grain size of ∼72 nm (773 K) and ∼80 nm (1173 K). DC-magnetization measurements under an applied magnetic field of H = ±60 kOe showed an increase in the magnetization with the increase of calcination temperature. Ferromagnetic nature shown by non-stoichiometric LaMnO{sub 3+δ} was verified by well-defined hysteresis loop with large remanent magnetization (M{sub r}) and coercive field (H{sub c}). Surface areas of LaMnO{sub 3+δ} nanoparticles were found to be 157.4 and 153 m{sup 2} g{sup −1} for the samples annealed at 773 K and 1173 K, respectively.« less
  • The reactions of Zn(NO{sub 3}){sub 2}·6H{sub 2}O with mixed ligands of 5-amino-tetrazole (Hatz) and l,2,4,5-benzenetetracarboxylic acid (H{sub 4}btec) under hydro(solvo)thermal conditions, gave two three-dimensional (3D) porous metal-organic frameworks (MOFs) of ([Zn{sub 3}(atz){sub 2}(btec)(DMF){sub 2}]·DMF·2H{sub 2}O){sub n} (1) and [Zn{sub 2}(Hprz)(atz)(btec)(H{sub 2}O)]{sub n} (2) in the absence and presence of piperazine (prz), respectively. 1 and 2 were characterized by infrared spectra (IR), elemental analyses (EA) and single-crystal/powder X-ray diffraction. In 1, the adjacent 1D [Zn{sub 3}(btec)]{sub n}{sup 2n+} chains are linked together by atz{sup −} ligands to form a 3D porous MOF with 1D tetragonal channels filled with coordinated and guestmore » DMF, and lattice water molecules. In 2, the adjacent 2D [Zn{sub 2}(btec)]{sub n} wavelike sheets are pillared through atz{sup −} ligands to generate a 3D layered-pillared porous MOF with 1D open channels, which are occupied by coordinated Hprz{sup +} cations and coordinated water molecules. Additionally, thermal stabilities and photoluminescent properties of both compounds in the solid-state at room temperature have been investigated and discussed in detail. - Graphical abstract: Two new MOFs constructed from Zn(II) salts with mixed ligands of 5-amino-tetrazole and l,2,4,5-benzenetetracarboxylic acid were synthesized under different reaction conditions. Structural diversities indicate that the reaction solvent system or the presence of organic base play crucial roles in modulating structures of these compounds. And more, their thermal stability and luminescence are also discussed. - Highlights: • Two new Zn(II) MOFs based on mixed ligands were synthesized. • The two Zn(II) MOFs exhibit different structural motifs. • The two Zn(II) MOFs are photoluminscent in the solid state at room temperature.« less