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Title: Crystal structures and thermodynamics/kinetics of Zn(II) coordination polymers with helical chains

Abstract

Solvothermal reactions of Zn(II) acetates and four V-shaped carboxylates ligands in the presence of 1,4-Bis(2-methyl-imidazol-1-yl)butane afforded four interesting Zn(II) coordination polymers with helical chains, namely, {[Zn(bib)(atibdc)]·2H_2O}{sub n} (1), {[Zn(bib)(atbip)]·H_2O}{sub n} (2), {[Zn(bib)(2,2′-tda)]}{sub n} (3) and {[Zn(bib)(5-tbipa)]·EtOH}{sub n} (4), (H{sub 2}atibdc=5-amino-2,4,6-triiodoisophthalic acid, H{sub 2}atbip=5-amino-2,4,6-tribromoisophthalic acid, 2,2′-H{sub 2}tad=2,2′-thiodiacetic acid, 5-H{sub 2}tbipa=5-tert-butyl-isophthalic acid). 1 reveals a 3D chiral framework with three kinds of helical chains along a, b and c axis. 2 shows a 2D step-type chiral framework with right-handed helical chains. 3 displays a wavelike 2D layer network possessing alternate left- and right-handed helical chains. 4 presents a four-connected 3D framework with zigzag and meso-helical chains. The different spacers and substituent group of carboxylic acid ligands may lead to the diverse network structures of 1–4. The fluorescent properties of complexes 1−4 were studied. In addition, the thermal decompositions properties of 1–4 were investigated by simultaneous TG/DTG–DSC technique. The apparent activation energy E and the pre-exponential factor (A) of skeleton collapse for the complexes 1–4 are calculated by the integral Kissinger's method and Ozawa–Doyle's method. The activation energy E (E{sub 1}=209.658 kJ·mol{sup −1}, E{sub 2}=250.037 kJ mol{sup −1}, E{sub 3}=225.300 kJ mol{sup −1}, E{sub 4}=186.529 kJ·mol{sup −1}) demonstrates that the reaction rate ofmore » the melting decomposition is slow. The thermodynamic parameters (ΔH{sup ‡}, ΔG{sup ‡} and ΔS{sup ‡}) at the peak temperatures of the DTG curves were also calculated. ΔG{sup ‡}>0 indicates that the skeleton collapse is not spontaneous. ΔH{sub d}>0 suggests that the skeleton collapse is endothermic, corresponding to the intense endothermic peak of the DSC curve. The structural stability could be illustrated from the point of thermodynamics and kinetics. - Graphical abstract: Four new zinc coordination architectures constructed from the primary ligand bib, transition metal ions Zn(II) and four V-shaped carboxylate coligands. The different structural evolutions of complexes 1–4 have systematically illustrated that the carboxylate coligands play a critical role in the assemblies of the CPs. Their thermal decompositions properties of 1–4 were investigated by simultaneous TG/DTG–DSC technique. The apparent activation energy E and the pre-exponential factor (A) of skeleton collapse for the complexes 1−4 are calculated by the integral Kissinger’s method and Ozawa–Doyle’s method. The structural stability could be illustrated from the point of thermodynamics and kinetics. Display Omitted.« less

Authors:
 [1];  [1]; ;  [1];  [2];  [1]
  1. Key Laboratory of Synthetic and Natural Functional Molecule Chemistry of the Ministry of Education, College of Chemistry and Materials Science, Northwest University, Xi’an 710069 (China)
  2. Shaanxi Key Laboratory of Comprehensive Utilization of Tailings Resources, College of Chemical Engineering and Modern Materials, Shangluo University, Shangluo 726000 (China)
Publication Date:
OSTI Identifier:
22584151
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 239; 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; ACTIVATION ENERGY; BUTANE; CALORIMETRY; CHIRALITY; CRYSTAL STRUCTURE; CRYSTALS; FLUORESCENCE; LIGANDS; POLYMERS; PYROLYSIS; REACTION KINETICS; SKELETON; STABILITY; THERMODYNAMICS; TRANSITION ELEMENTS

Citation Formats

He, Tian, Yue, Ke-Fen, E-mail: ykflyy@nwu.edu.cn, Zhao, Yi-xing, Chen, San-Ping, Zhou, Chun-sheng, E-mail: slzhoucs@126.com.cn, and Yan, Ni. Crystal structures and thermodynamics/kinetics of Zn(II) coordination polymers with helical chains. United States: N. p., 2016. Web. doi:10.1016/J.JSSC.2016.04.022.
He, Tian, Yue, Ke-Fen, E-mail: ykflyy@nwu.edu.cn, Zhao, Yi-xing, Chen, San-Ping, Zhou, Chun-sheng, E-mail: slzhoucs@126.com.cn, & Yan, Ni. Crystal structures and thermodynamics/kinetics of Zn(II) coordination polymers with helical chains. United States. doi:10.1016/J.JSSC.2016.04.022.
He, Tian, Yue, Ke-Fen, E-mail: ykflyy@nwu.edu.cn, Zhao, Yi-xing, Chen, San-Ping, Zhou, Chun-sheng, E-mail: slzhoucs@126.com.cn, and Yan, Ni. 2016. "Crystal structures and thermodynamics/kinetics of Zn(II) coordination polymers with helical chains". United States. doi:10.1016/J.JSSC.2016.04.022.
@article{osti_22584151,
title = {Crystal structures and thermodynamics/kinetics of Zn(II) coordination polymers with helical chains},
author = {He, Tian and Yue, Ke-Fen, E-mail: ykflyy@nwu.edu.cn and Zhao, Yi-xing and Chen, San-Ping and Zhou, Chun-sheng, E-mail: slzhoucs@126.com.cn and Yan, Ni},
abstractNote = {Solvothermal reactions of Zn(II) acetates and four V-shaped carboxylates ligands in the presence of 1,4-Bis(2-methyl-imidazol-1-yl)butane afforded four interesting Zn(II) coordination polymers with helical chains, namely, {[Zn(bib)(atibdc)]·2H_2O}{sub n} (1), {[Zn(bib)(atbip)]·H_2O}{sub n} (2), {[Zn(bib)(2,2′-tda)]}{sub n} (3) and {[Zn(bib)(5-tbipa)]·EtOH}{sub n} (4), (H{sub 2}atibdc=5-amino-2,4,6-triiodoisophthalic acid, H{sub 2}atbip=5-amino-2,4,6-tribromoisophthalic acid, 2,2′-H{sub 2}tad=2,2′-thiodiacetic acid, 5-H{sub 2}tbipa=5-tert-butyl-isophthalic acid). 1 reveals a 3D chiral framework with three kinds of helical chains along a, b and c axis. 2 shows a 2D step-type chiral framework with right-handed helical chains. 3 displays a wavelike 2D layer network possessing alternate left- and right-handed helical chains. 4 presents a four-connected 3D framework with zigzag and meso-helical chains. The different spacers and substituent group of carboxylic acid ligands may lead to the diverse network structures of 1–4. The fluorescent properties of complexes 1−4 were studied. In addition, the thermal decompositions properties of 1–4 were investigated by simultaneous TG/DTG–DSC technique. The apparent activation energy E and the pre-exponential factor (A) of skeleton collapse for the complexes 1–4 are calculated by the integral Kissinger's method and Ozawa–Doyle's method. The activation energy E (E{sub 1}=209.658 kJ·mol{sup −1}, E{sub 2}=250.037 kJ mol{sup −1}, E{sub 3}=225.300 kJ mol{sup −1}, E{sub 4}=186.529 kJ·mol{sup −1}) demonstrates that the reaction rate of the melting decomposition is slow. The thermodynamic parameters (ΔH{sup ‡}, ΔG{sup ‡} and ΔS{sup ‡}) at the peak temperatures of the DTG curves were also calculated. ΔG{sup ‡}>0 indicates that the skeleton collapse is not spontaneous. ΔH{sub d}>0 suggests that the skeleton collapse is endothermic, corresponding to the intense endothermic peak of the DSC curve. The structural stability could be illustrated from the point of thermodynamics and kinetics. - Graphical abstract: Four new zinc coordination architectures constructed from the primary ligand bib, transition metal ions Zn(II) and four V-shaped carboxylate coligands. The different structural evolutions of complexes 1–4 have systematically illustrated that the carboxylate coligands play a critical role in the assemblies of the CPs. Their thermal decompositions properties of 1–4 were investigated by simultaneous TG/DTG–DSC technique. The apparent activation energy E and the pre-exponential factor (A) of skeleton collapse for the complexes 1−4 are calculated by the integral Kissinger’s method and Ozawa–Doyle’s method. The structural stability could be illustrated from the point of thermodynamics and kinetics. Display Omitted.},
doi = {10.1016/J.JSSC.2016.04.022},
journal = {Journal of Solid State Chemistry},
number = ,
volume = 239,
place = {United States},
year = 2016,
month = 7
}
  • Two 3D coordination polymers with different structure motifs, [Zn{sub 2}(PCPA){sub 2}(IN){sub 2}] {sub n} (1) and [Co(PCPA)(IN)] {sub n} (2) (PCPA=p-chlorophenoxyacetate, IN=isonicotinate), first constructed from mixed rigid and flexible carboxylate ligands, have been obtained under hydrothermal condition and characterized by elemental analyses, IR spectra, thermogravimetric analysis, fluorescent spectra and single crystal X-ray diffraction analysis. The most intriguing structural feature is that each complex exhibits both infinite helical Zn({mu} {sub 2}-carboxylate) or Co({mu} {sub 3}-carboxylates) chain units with 2{sub 1} helices and zigzag M {sub 2}(IN){sub 2} (M=zinc and cobalt) chain units by reason of two different carboxylate ligands coordinating tomore » metal centers. Additionally, compounds 1 and 2 show similar blue fluorescence in the solid state at room temperature.« less
  • Two zinc coordination polymers {[Zn_2(TPPBDA)(oba)_2]·DMF·1.5H_2O}{sub n} (1), {[Zn(TPPBDA)_1_/_2(tpdc)]·DMF}{sub n} (2) have been synthesized by zinc metal salt, nanosized tetradentate pyridine ligand with flexible or rigid V-shaped carboxylate co-ligands. These complexes were characterized by elemental analyses and X-ray single-crystal diffraction analyses. Compound 1 is a 2-fold interpenetrated 3D framework with [Zn{sub 2}(CO{sub 2}){sub 4}] clusters. Compound 2 can be defined as a five folded interpenetrating bbf topology with mononuclear Zn{sup 2+}. These mononuclear or dinuclear cluster units are linked by mix-ligands, resulting in various degrees of interpenetration. In addition, the photoluminescent properties for TPPBDA ligand under different state and coordination polymersmore » have been investigated in detail. - Graphical abstract: Two zinc coordination polymers have been synthesized by zinc metal salt, nanosized tetradentate pyridine ligand with flexible or rigid V-shaped carboxylate co-ligands. Compound 1 is a 2-fold interpenetrated 3D framework with [Zn{sub 2}(CO{sub 2}){sub 4}] clusters. Compound 2 can be defined as a five folded interpenetrating bbf topology with mononuclear Zn{sup 2+}. In addition, the photoluminescent properties for TPPBDA ligand under different status and coordination polymers have been investigated in detail. Display Omitted - Highlights: • Two Zn coordination polymers based on mononuclear or dinuclear cluster units have been synthesized. • Compound 1 is a 2-fold interpenetrated 3D framework with [Zn{sub 2}(CO{sub 2}){sub 4}] clusters. • Compound 2 is a five folded interpenetrating bbf topology with mononuclear Zn{sup 2+}. • The photoluminescent properties for TPPBDA with different state and two coordination polymers have been investigated.« less
  • The hydrothermal reactions of MnCl{sub 2}.4H{sub 2}O, 3,4-pyridinedicarboxylic acid (3,4-pydaH{sub 2}) and triethylamine in aqueous medium yield two 3D metal-organic hybrid materials, [Mn(3,4-pyda)] (1) and [Mn{sub 3}(OH){sub 2}(3,4-pyda){sub 2}(H{sub 2}O){sub 2}] (2), respectively. In both complexes, each 3,4-pyda acts as a pentadentate ligand to connect five Mn(II) atoms via the pyridyl group and the two {mu}{sub 2}-carboxylate groups (one in syn,anti-mode and one in syn-syn mode for 1 and both in syn,anti-mode for 2). Complex 1 possesses an interesting 3D coordination polymeric structure incorporating 1D helical Mn({mu}{sub 2}-carboxylate){sub 2} chain units, in which each Mn(II) atom is coordinated in lessmore » common square pyramidal geometry to four carboxylato oxygen atoms and one pyridyl nitrogen atom. Each 3,4-pyda links three helical Mn({mu}{sub 2}-carboxylate){sub 2} chains and each Mn({mu}{sub 2}-carboxylate){sub 2} chain is linked by other eight helical Mn({mu}{sub 2}-carboxylate){sub 2} chains via sharing 3,4-pyda bridges. Complex 2 is a 3D coordination network consisting of 1D Mn{sub 3}(OH){sub 2} chains and 3,4-pyda bridges. The repeating trimeric structural unit in the manganese(II) hydroxide chain consists of two edge-sharing symmetry-related manganese octahedra linked via {mu}{sub 3}-OH to a vertex of Mn{sub 2} octahedron. Each 3,4-pyda links three Mn{sub 3}(OH){sub 2} chains and each Mn{sub 3}(OH){sub 2} chain is linked by other six Mn{sub 3}(OH){sub 2} chains via 3,4-pyda bridges, resulting in a 3D coordination solid. Magnetic measurements reveal that a weak antiferromagnetic interaction between the Mn{sup II} ions occurs in complex 1 and a 3D magnetic ordering at about 7.0K in complex 2.« less
  • A series of lanthanide coordination polymers, (Him){sub n}[Ln(ip){sub 2}(H{sub 2}O)]{sub n} [Ln=La(1), Pr(2), Nd(3) and Dy(4), H{sub 2}ip=isophthalic acid, im=imidazole] and [Y{sub 2}(ip){sub 3}(H{sub 2}O){sub 2}]{sub n}.nH{sub 2}O (5), have been synthesized and characterized by elemental analyses, infrared (IR), ultraviolet-visible-near infrared (UV-Vis-NIR) and single-crystal X-ray diffraction analyses. The isostructural compounds 1-4 possess 3-D structures with three different kinds of channels. Compound 5 features a 2-D network making of two different kinds of quadruple-helical chains. Compounds 2 and 3 present the characteristic emissions of Pr(III) and Nd(III) ions in NIR region, respectively. Compound 4 shows sensitized luminescence of Dy(III) ions inmore » visible region. - Graphical abstract: A series of lanthanide coodination polymers, (Him){sub n}[Ln(ip){sub 2}(H{sub 2}O)]{sub n} [Ln=La(1), Pr(2), Nd(3) and Dy(4)] and [Y{sub 2}(ip){sub 3}(H{sub 2}O){sub 2}]{sub n}.nH{sub 2}O (5), have been reported. The isostructural compounds 1-4 possess 3-D structures with three different kinds of channels. Compound 5 displays a 2-D network making of two kinds of quadruple-helical chains. Display Omitted.« less
  • Six new coordination polymers, namely, [Pb(L)(H{sub 2}O)] (1), [Pb(L)(phen)] (2), [Pb{sub 2}(L){sub 2}(4,4′-bipy){sub 0.5}] (3), [Cd(L)(phen)] (4), [Cd(L)(4,4′-bipy)]·H{sub 2}O (5) and [Mn(L)(4,4′-bipy)]·H{sub 2}O (6) have been synthesized by the hydrothermal reaction of 2,2′-[hexafluoroisopropylidenebis(p-phenyleneoxy)]diacetic acid (H{sub 2}L) with Pb(II)/Cd(II)/Mn(II) in the presence of ancillary ligands 4,4′-bipyridine (4,4′-bipy) or 1,10-phenanthroline (phen). Complexes 1 and 4–6 exhibit 2-D structures, and complexes 2–3 display 3-D frameworks, of which L{sup 2−} ligands join metal ions to single-stranded helical chains of 1, 3–6 and double-stranded helical chains of 2. Complexes 2 and 3 also contain double-stranded Metal–O helices. Topology analysis reveals that complexes 1 and 4more » both represent 4-connected sql net, 2 represents 6-connected pcu net, 3 exhibits a novel (3,12)-connected net, while 5 and 6 display (3,5)-connected gek1 net. The six complexes exhibit two kinds of inorganic–organic connectivities: I{sup 0}O{sup 2} for 1, 4–6, and I{sup 1}O{sup 2} for 2–3. The photoluminescent properties of 4–5 and the magnetic properties of 6 have been investigated. - Graphical abstract: Six new Pb(II)/Cd(II)/Mn(II) coordination polymers with helical structures based on flexible V-shaped dicarboxylate ligand have been synthesized and structurally characterized. Photoluminescent and magnetic properties have been investigated. - Highlights: • Six novel M(II) coordination polymers with 2,2′-[hexafluoroisopropylidenebis(p-phenyleneoxy)]diacetic acid and N-donor ligands. • Complexes 1–6 show diverse intriguing helical characters. • The luminescent properties of complexes 1–5 were investigated. • Complex 6 shows antiferromagnetic coupling.« less