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

Title: Synthesis and structural characterization of three copper coordination polymers with pyridine derivatives from hydro(solvo)thermal in situ decarboxylation reactions of 2,5-dicarboxylpyridine

Abstract

The hydro(solvo)thermal self-assembles of CuI, KI and 2,5-dicarboxylpyridine [2,5-(COOH){sub 2}py] in different molar ratios in H{sub 2}O/alcohol solutions produced three Cu coordination polymers as 2-D [N-C{sub 2}H{sub 5}py][Cu{sub 3}I{sub 4}] 1, 1-D [N-CH{sub 3}py][Cu{sub 2}I{sub 3}] 2 as well as 1-D [Cu(2-COOpy){sub 2}]{center_dot}H{sub 2}O 3 (N-C{sub 2}H{sub 5}py=N-ethylpyridine, N-CH{sub 3}py=N-methylpyridine, 2-COOpy=2-carboxylpyridine). N-C{sub 2}H{sub 5}py in 1 and N-CH{sub 3}py in 2 derived from the solvothermal in situ simultaneous decarboxylation and N-alkylation reactions of 2,5-(COOH){sub 2}py. The semi-decarboxylation reaction of 2,5-(COOH){sub 2}py into 2-COOpy occurred in the preparation of 3. X-ray single-crystal analysis revealed that CuI is transformed into a 2-D [Cu{sub 3}I{sub 4}]{sup -} layer in compound 1 and a 1-D chain in compound 2, templated by [N-C{sub 2}H{sub 5}py]{sup +} and [N-CH{sub 3}py]{sup +}, respectively. Compound 3 is a divalent Cu compound. The Cu(II) centers with a 4+2 geometry are coordinated by {mu}{sub 3}-mode 2-COOpy ligands. All of the title compounds were characterized by CHN analysis, IR spectrum analysis and TG analysis. Compounds 1 and 2 exhibit fluorescence properties with the maximum emissions at 581 nm for 1 and 537 nm for 2. - Graphical abstract: Three compounds were obtained via in situ metal-ligand hydro(solvo)thermal reactions of 2,5-(cooh){sub 2}pymore » with cui. Three types of in situ reactions occurred for 2,5-(cooh){sub 2}py: decarboxylation n-ethylated in 1, n-methylated in 2 and semi-decarboxylation in 3.« less

Authors:
;  [1];  [1];  [2]; ;  [1];  [1]
  1. College of Chemistry and State Key Laboratory of Inorganic Synthesis and Preparative Chemistry, Jilin University, Changchun 130023 (China)
  2. (China)
Publication Date:
OSTI Identifier:
21421546
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 183; Journal Issue: 7; Other Information: DOI: 10.1016/j.jssc.2010.04.033; PII: S0022-4596(10)00180-5; Copyright (c) 2010 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; 36 MATERIALS SCIENCE; ALKYLATION; COPPER COMPLEXES; COPPER IODIDES; DECARBOXYLATION; FLUORESCENCE; INFRARED SPECTRA; LIGANDS; MONOCRYSTALS; POLYMERS; POTASSIUM IODIDES; PYRIDINE; SOLUTIONS; SYNTHESIS; THERMAL GRAVIMETRIC ANALYSIS; WATER; ALKALI METAL COMPOUNDS; AZINES; CHEMICAL ANALYSIS; CHEMICAL REACTIONS; COMPLEXES; COPPER COMPOUNDS; COPPER HALIDES; CRYSTALS; DISPERSIONS; EMISSION; GRAVIMETRIC ANALYSIS; HALIDES; HALOGEN COMPOUNDS; HETEROCYCLIC COMPOUNDS; HOMOGENEOUS MIXTURES; HYDROGEN COMPOUNDS; INORGANIC PHOSPHORS; IODIDES; IODINE COMPOUNDS; LUMINESCENCE; MIXTURES; ORGANIC COMPOUNDS; ORGANIC NITROGEN COMPOUNDS; OXYGEN COMPOUNDS; PHOSPHORS; PHOTON EMISSION; POTASSIUM COMPOUNDS; PYRIDINES; QUANTITATIVE CHEMICAL ANALYSIS; SPECTRA; THERMAL ANALYSIS; TRANSITION ELEMENT COMPLEXES; TRANSITION ELEMENT COMPOUNDS

Citation Formats

Hou Qin, Xu Jianing, Yu Jiehui, E-mail: jiehuiyu@yahoo.com.c, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, Jiangsu 210093, Wang Tiegang, Yang Qingfeng, and Xu Jiqing, E-mail: xjq@mail.jlu.edu.c. Synthesis and structural characterization of three copper coordination polymers with pyridine derivatives from hydro(solvo)thermal in situ decarboxylation reactions of 2,5-dicarboxylpyridine. United States: N. p., 2010. Web.
Hou Qin, Xu Jianing, Yu Jiehui, E-mail: jiehuiyu@yahoo.com.c, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, Jiangsu 210093, Wang Tiegang, Yang Qingfeng, & Xu Jiqing, E-mail: xjq@mail.jlu.edu.c. Synthesis and structural characterization of three copper coordination polymers with pyridine derivatives from hydro(solvo)thermal in situ decarboxylation reactions of 2,5-dicarboxylpyridine. United States.
Hou Qin, Xu Jianing, Yu Jiehui, E-mail: jiehuiyu@yahoo.com.c, State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, Jiangsu 210093, Wang Tiegang, Yang Qingfeng, and Xu Jiqing, E-mail: xjq@mail.jlu.edu.c. 2010. "Synthesis and structural characterization of three copper coordination polymers with pyridine derivatives from hydro(solvo)thermal in situ decarboxylation reactions of 2,5-dicarboxylpyridine". United States. doi:.
@article{osti_21421546,
title = {Synthesis and structural characterization of three copper coordination polymers with pyridine derivatives from hydro(solvo)thermal in situ decarboxylation reactions of 2,5-dicarboxylpyridine},
author = {Hou Qin and Xu Jianing and Yu Jiehui, E-mail: jiehuiyu@yahoo.com.c and State Key Laboratory of Coordination Chemistry, Nanjing University, Nanjing, Jiangsu 210093 and Wang Tiegang and Yang Qingfeng and Xu Jiqing, E-mail: xjq@mail.jlu.edu.c},
abstractNote = {The hydro(solvo)thermal self-assembles of CuI, KI and 2,5-dicarboxylpyridine [2,5-(COOH){sub 2}py] in different molar ratios in H{sub 2}O/alcohol solutions produced three Cu coordination polymers as 2-D [N-C{sub 2}H{sub 5}py][Cu{sub 3}I{sub 4}] 1, 1-D [N-CH{sub 3}py][Cu{sub 2}I{sub 3}] 2 as well as 1-D [Cu(2-COOpy){sub 2}]{center_dot}H{sub 2}O 3 (N-C{sub 2}H{sub 5}py=N-ethylpyridine, N-CH{sub 3}py=N-methylpyridine, 2-COOpy=2-carboxylpyridine). N-C{sub 2}H{sub 5}py in 1 and N-CH{sub 3}py in 2 derived from the solvothermal in situ simultaneous decarboxylation and N-alkylation reactions of 2,5-(COOH){sub 2}py. The semi-decarboxylation reaction of 2,5-(COOH){sub 2}py into 2-COOpy occurred in the preparation of 3. X-ray single-crystal analysis revealed that CuI is transformed into a 2-D [Cu{sub 3}I{sub 4}]{sup -} layer in compound 1 and a 1-D chain in compound 2, templated by [N-C{sub 2}H{sub 5}py]{sup +} and [N-CH{sub 3}py]{sup +}, respectively. Compound 3 is a divalent Cu compound. The Cu(II) centers with a 4+2 geometry are coordinated by {mu}{sub 3}-mode 2-COOpy ligands. All of the title compounds were characterized by CHN analysis, IR spectrum analysis and TG analysis. Compounds 1 and 2 exhibit fluorescence properties with the maximum emissions at 581 nm for 1 and 537 nm for 2. - Graphical abstract: Three compounds were obtained via in situ metal-ligand hydro(solvo)thermal reactions of 2,5-(cooh){sub 2}py with cui. Three types of in situ reactions occurred for 2,5-(cooh){sub 2}py: decarboxylation n-ethylated in 1, n-methylated in 2 and semi-decarboxylation in 3.},
doi = {},
journal = {Journal of Solid State Chemistry},
number = 7,
volume = 183,
place = {United States},
year = 2010,
month = 7
}
  • A new three-dimensional open-framework gallophosphate: [H{sub 3}N(CH{sub 2}){sub 2}NH{sub 3}]{sub 1/2}.[Ga{sub 5} (PO{sub 4}){sub 4}(OH){sub 4}] has been prepared by hydro(solvo)thermal synthesis in presence of ethylenediamine (en) as structure-directing agent. Its structure was determined by means of single-crystal X-ray diffraction analysis with the following crystal data: monoclinic space group C2/m, a=10.1604(9)A, b=12.0085(15)A, c=7.1892(7)A, {beta}=90.797(6){sup o}, V=877.08(16)A{sup 3}, Z=2, R{sub 1}=0.0264, wR{sub 2}=0.0764. The total numbers of measured reflections and unique reflections were 3508 and 1300, respectively. It is built up from a new secondary building unit (SBU) Ga{sub 4}P{sub 4}O{sub 20}(OH){sub 4}, in which Ga atoms exhibit distorted trigonal bipyramidalmore » coordination and P atoms are in tetrahedral coordination. The SBU Ga{sub 4}P{sub 4}O{sub 20}(OH){sub 4} are linked into a layer by bridge oxygen atoms. The GaO{sub 4}(OH){sub 2} octahedra link the layers into a three-dimentional framework. Diprotonated ethylenediamine was found in the channel of the framework. The material was characterized by IR spectroscopy, {sup 1}H NMR spectra, thermogravimetric and differential thermal analyses and elemental analysis.« less
  • Two copper helical coordination polymers, [Cu(2-pc)(3-pc)]{sub n}1 and [Cu(2-pc)(4-pc)]{sub n}2 (2-pc=2-pyridine carboxylate, 3-pc=3-pyridine carboxylate, 4-pc=4-pyridine carboxylate) have been hydrothermally synthesized directly from pyridine carboxylic acids and copper nitrate. The crystal structure were determined by single-crystal X-ray diffraction with the following data: compound 1, orthorhombic, P2{sub 1}2{sub 1}2{sub 1}, a=6.591(3) A, b=8.692(5) A, c=20.548(9) A, V=1177.2(9) A{sup 3}, Z=4; compound 2, orthorhombic, Pna2{sub 1}, a=21.160(10) A, b=9.095(5) A, c=6.401(3) A, V=1231.9(11) A{sup 3}, Z=4. The acentric three-dimensional (3D) framework of 1 is constructed from right-handed helical Cu(2-pc) chains and left-handed Cu(3-pc) helices. As for 2, Cu(2-pc) helical chains, in which left-more » and right-handed helices are coexisting, and Cu(4-pc) zigzag chains combined together to form acentric 3D architecture of 2 as well. Additionally, besides general spectral characterization, we first introduce generalized 2D correlation spectroscopy to explore the coordination polymers and ascertain the stretching vibration location of carboxylate groups of compounds 1 and 2. -- Abstract: Two copper helical coordination polymers, [Cu(2-pc)(3-pc)]{sub n}1 and [Cu(2-pc)(4-pc)]{sub n}2 have been obtained by hydrothermal synthesis. Both two compounds crystallized in non-centrosymmetric space groups, P2{sub 1}2{sub 1}2{sub 1} and Pna2{sub 1}, respectively. The 3D framework of 1 is constructed from right-handed helical Cu(2-pc) chains and left-handed Cu(3-pc) helices. As for 2, Cu(2-pc) helical chains, in which left- and right-handed helices are coexisting, and Cu(4-pc) zigzag chains combined together to form 3D architecture of 2 as well.« less
  • We have successfully prepared crystals of thiazole-5-carboxylic acid (5-Htza) (L) and three new thiazole-5-carboxylate-based Cu{sup 2+} coordination polymers with different dimensionality, namely, 1D [Cu{sub 2}(5-tza){sub 2}(1,10-phenanthroline){sub 2}(NO{sub 3}){sub 2}] (1), 2D [Cu(5-tza){sub 2}(MeOH){sub 2}] (2), and 3D [Cu(5-tza){sub 2}]·H{sub 2}O (3). These have been characterized by single crystal X-ray diffraction and thermogravimetry. Interestingly, the 2D network structure of 2 can directly transform into the 3D framework of 3 upon removal of methanol molecules at room temperature. 2 can also undergo structural transformation to produce the same 2D network present in the known [Cu(5-tza){sub 2}]·1.5H{sub 2}O upon heat treatment for 2more » h. This 2D network can adsorb water and convert to 3 upon exposure to air. - Highlights: • Rare examples of coordination polymers of thiazole-5-carboxylic acid were prepared. • Non-covalent interactions play a key role on the assembly of the complexes in solid state. • Structural transformation of a 2D framework to a 3D upon removal of methanol is observed.« less
  • We present a study of two new solvothermal synthesis approaches to mixed-metal oxide materials and structural characterisation of the products formed. The solvothermal oxidation of metallic gallium by a diethanolamine solution of iron(II) chloride at 240 °C produces a crystalline sample of a spinel-structured material, made up of nano-scale particles typically 20 nm in dimension. XANES spectroscopy at the K-edge shows that the material contains predominantly Fe{sup 2+} in an octahedral environment, but that a small amount of Fe{sup 3+} is also present. Careful analysis using transmission electron microscopy and powder neutron diffraction shows that the sample is actually amore » mixture of two spinel materials: predominantly (>97%) an Fe{sup 2+} phase Ga{sub 1.8}Fe{sub 1.2}O{sub 3.9}, but with a minor impurity phase that is iron-rich. In contrast, the hydrothermal reaction of titanium bis(ammonium lactato)dihydroxide in water with increasing amounts of Sn(IV) acetate allows nanocrystalline samples of the SnO{sub 2}–TiO{sub 2} solid solution to be prepared directly, as proved by powder XRD and Raman spectroscopy. - Graphical abstract: New solvothermal synthesis approaches to spinel and rutile mixed-metal oxides are reported. - Highlights: • Solvothermal oxidation of gallium metal in organic iron(II) solution gives a novel iron gallate spinel. • Hydrothermal reaction of titanium(IV) complex and tin(IV) acetate produces the complete SnO{sub 2}–TiO{sub 2} solid solution. • Nanostructured mixed-metal oxide phases are produced directly from solution.« less
  • A series of 3d-4f heterometallic coordination polymers, formulated as {l_brace} [Cu{sub 3}Ln{sub 2}(pydc){sub 6}(H{sub 2}O){sub 12}]{center_dot}4H{sub 2}O{r_brace} {sub n} [Ln=Tb (1), Eu (2), Dy (3), Ho (4), Lu (5)], {l_brace} [CuNd{sub 2}(pydc){sub 4}(H{sub 2}O){sub 3}]{center_dot}H{sub 2}O{r_brace} {sub n} (6) and {l_brace} [Cu{sub 3}Pr{sub 2}(pydc){sub 6}(H{sub 2}O){sub 13}]{center_dot}4H{sub 2}O{r_brace} {sub n} (7) (where H{sub 2}pydc=pyridine-2,5-dicarboxylic acid), have been hydrothermally prepared by reactions of H{sub 2}pydc ligand with lanthanide ions in the presence of Cu(II) ion. X-ray crystal structure analysis reveals that these compounds exhibit rich structural chemistry. 1-5 are isomorphous and present a two-dimensional network constructed from Ln{sub 2}Cu{sub 2}L{sub 2}(H{submore » 2}O){sub 2} SBU rings and CuL{sub 2}(H{sub 2}O) building blocks. In 6, two-dimensional ladder-like layers based on Nd(III) belts and CuL{sub 2}O{sub 2} units are assembled by H{sub 2}pydc ligands into a three-dimensional open framework. Polymer 7 displays a two-dimensional wave-like layer structure containing two distinct ring units, in which a new coordination mode of the pydc{sup 2-} ligand is observed. The results indicate that the coordination flexibility of the pydc{sup 2-} ligand and lanthanide contraction effect play cooperative roles in the formation of coordination polymers with different polymeric architectures. Compounds 1-2 exhibit intense green and red luminescence emission characteristics of Tb(III) and Eu(III), respectively. Furthermore, elemental analyses (EA), infrared spectra (IR) and thermogravimetric analyses (TGA) of these compounds were also studied. - Graphical abstract: Seven 3d-4f heterometallic coordination polymers were synthesized by reactions of H{sub 2}pydc with lanthanide metal ions in the presence of Cu{sup 2+}, the effects of Cu{sup 2+} on the structures and photoluminescent properties of Ln-pydc{sup 2-} systems were investigated. Highlights: Black-Right-Pointing-Pointer Seven 3d-4f heterometallic compounds have been prepared and characterized. Black-Right-Pointing-Pointer 1-5 and 7 are constructed from Ln{sub 2}Cu{sub 2}L{sub 2}(H{sub 2}O){sub 2} rings and CuL{sub 2}(H{sub 2}O) building blocks. Black-Right-Pointing-Pointer One new coordination mode of the pydc{sup 2-} ligand is first observed. Black-Right-Pointing-Pointer 1-2 exhibit intense characteristic luminescence emission spectra of lanthanide ions.« less