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Title: Syntheses and crystal structures of a series of new divalent metal phosphonates with imino-bis(methylphosphonic acid)

Abstract

Hydrothermal reactions of divalent transition metal salts with imino-bis(methylphosphonic acid), NH(CH{sub 2}PO{sub 3}H{sub 2}){sub 2} (H{sub 4}L) afforded three new metal phosphonates, namely, Cu[NH(CH{sub 2}PO{sub 3}H){sub 2}] 1, {l_brace}Co[NH{sub 2}(CH{sub 2}PO{sub 3}H)(CH{sub 2}PO{sub 3})](H{sub 2}O){sub 2}{r_brace}.H{sub 2}O 2 and Mn[NH{sub 2}(CH{sub 2}PO{sub 3}H)(CH{sub 2}PO{sub 3})](H{sub 2}O) 3. When HO{sub 2}C(CH{sub 2}){sub 3}N(CH{sub 2}PO{sub 3}H{sub 2}){sub 2} was used as the phosphonate ligand and 4,4'-bipy as the second metal linker, {l_brace}Cu{sub 4}[NH(CH{sub 2}PO{sub 3}){sub 2}]{sub 2}(4,4'-bipy)(H{sub 2}O){sub 4}{r_brace}.9H{sub 2}O 4 with a pillared layered architecture was obtained. The NH(CH{sub 2}PO{sub 3}){sub 2} anion resulted from the cleavage of the HO{sub 2}C(CH{sub 2}){sub 3}-group during the reaction. Although compounds 1-3 have a same M/L ratio (1:1), they exhibit totally different structures.Compound 1 has a linear chain structure, in which each pair of square-pyramidal coordinated copper(II) ions are bridged by two phosphonate oxygen atoms to form a Cu{sub 2}O{sub 2} dimeric unit, and such dimeric units are further interconnected via phosphonate groups to form a [010] chain. Compound 2 has a layered architecture built from CoO{sub 6} octahedra bridged by phosphonate ligands. In compound 3, the interconnection of the manganese(II) ions by bridging imino-diphosphonate ligands leads to a 3D network. Compound 4 hasmore » a pillar-layered structure, the layers composed of Cu(II) ions bridged by aminodiphosphonate ligands are interconnected by 4,4'-bipy ligands to form channels along c-axis. Several factors that affect the structures of the metal phosphonates formed have also been discussed. Compounds 2 and 3 show predominant antiferromagnetic interactions between magnetic centers. -- Graphical abstract: Four new metal phosphonates, namely, Cu[NH(CH{sub 2}PO{sub 3}H){sub 2}] 1, {l_brace}Co[NH{sub 2}(CH{sub 2}PO{sub 3}H)(CH{sub 2}PO{sub 3})](H{sub 2}O){sub 2}{r_brace}.H{sub 2}O 2, Mn[NH{sub 2}(CH{sub 2}PO{sub 3}H)(CH{sub 2}PO{sub 3})](H{sub 2}O) 3 and {l_brace}Cu{sub 4}[NH(CH{sub 2}PO{sub 3}){sub 2}]{sub 2}(4,4'-bipy)(H{sub 2}O){sub 4}{r_brace}.9H{sub 2}O 4 have been synthesized and structurally characterized. Compound 1 has a linear chain structure, and compound 2 is layered. Compound 3 is three dimensional whereas compound 4 has a pillar-layered structure. Compounds 2 and 3 show predominant antiferromagnetic interactions between magnetic centers.« less

Authors:
 [1];  [2];  [2];  [3]
  1. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002 (China)
  2. Department of Chemistry, Texas A and M University, P.O. Box 30012, College Station, TX 77843-3012 (United States)
  3. State Key Laboratory of Structural Chemistry, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002 (China). E-mail: mjg@ms.fjirsm.ac.cn
Publication Date:
OSTI Identifier:
20784847
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 179; Journal Issue: 1; Other Information: DOI: 10.1016/j.jssc.2005.10.015; PII: S0022-4596(05)00475-5; Copyright (c) 2005 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; COPPER COMPOUNDS; COPPER IONS; CRYSTAL STRUCTURE; HYDROTHERMAL SYNTHESIS; LIGANDS; MAGNETIC PROPERTIES; MANGANESE COMPOUNDS; PHOSPHONATES

Citation Formats

Yang Bingping, Prosvirin, Andrey V., Zhao, Han-Hua, and Mao, Jiang-Gao. Syntheses and crystal structures of a series of new divalent metal phosphonates with imino-bis(methylphosphonic acid). United States: N. p., 2006. Web. doi:10.1016/j.jssc.2005.10.015.
Yang Bingping, Prosvirin, Andrey V., Zhao, Han-Hua, & Mao, Jiang-Gao. Syntheses and crystal structures of a series of new divalent metal phosphonates with imino-bis(methylphosphonic acid). United States. doi:10.1016/j.jssc.2005.10.015.
Yang Bingping, Prosvirin, Andrey V., Zhao, Han-Hua, and Mao, Jiang-Gao. Sun . "Syntheses and crystal structures of a series of new divalent metal phosphonates with imino-bis(methylphosphonic acid)". United States. doi:10.1016/j.jssc.2005.10.015.
@article{osti_20784847,
title = {Syntheses and crystal structures of a series of new divalent metal phosphonates with imino-bis(methylphosphonic acid)},
author = {Yang Bingping and Prosvirin, Andrey V. and Zhao, Han-Hua and Mao, Jiang-Gao},
abstractNote = {Hydrothermal reactions of divalent transition metal salts with imino-bis(methylphosphonic acid), NH(CH{sub 2}PO{sub 3}H{sub 2}){sub 2} (H{sub 4}L) afforded three new metal phosphonates, namely, Cu[NH(CH{sub 2}PO{sub 3}H){sub 2}] 1, {l_brace}Co[NH{sub 2}(CH{sub 2}PO{sub 3}H)(CH{sub 2}PO{sub 3})](H{sub 2}O){sub 2}{r_brace}.H{sub 2}O 2 and Mn[NH{sub 2}(CH{sub 2}PO{sub 3}H)(CH{sub 2}PO{sub 3})](H{sub 2}O) 3. When HO{sub 2}C(CH{sub 2}){sub 3}N(CH{sub 2}PO{sub 3}H{sub 2}){sub 2} was used as the phosphonate ligand and 4,4'-bipy as the second metal linker, {l_brace}Cu{sub 4}[NH(CH{sub 2}PO{sub 3}){sub 2}]{sub 2}(4,4'-bipy)(H{sub 2}O){sub 4}{r_brace}.9H{sub 2}O 4 with a pillared layered architecture was obtained. The NH(CH{sub 2}PO{sub 3}){sub 2} anion resulted from the cleavage of the HO{sub 2}C(CH{sub 2}){sub 3}-group during the reaction. Although compounds 1-3 have a same M/L ratio (1:1), they exhibit totally different structures.Compound 1 has a linear chain structure, in which each pair of square-pyramidal coordinated copper(II) ions are bridged by two phosphonate oxygen atoms to form a Cu{sub 2}O{sub 2} dimeric unit, and such dimeric units are further interconnected via phosphonate groups to form a [010] chain. Compound 2 has a layered architecture built from CoO{sub 6} octahedra bridged by phosphonate ligands. In compound 3, the interconnection of the manganese(II) ions by bridging imino-diphosphonate ligands leads to a 3D network. Compound 4 has a pillar-layered structure, the layers composed of Cu(II) ions bridged by aminodiphosphonate ligands are interconnected by 4,4'-bipy ligands to form channels along c-axis. Several factors that affect the structures of the metal phosphonates formed have also been discussed. Compounds 2 and 3 show predominant antiferromagnetic interactions between magnetic centers. -- Graphical abstract: Four new metal phosphonates, namely, Cu[NH(CH{sub 2}PO{sub 3}H){sub 2}] 1, {l_brace}Co[NH{sub 2}(CH{sub 2}PO{sub 3}H)(CH{sub 2}PO{sub 3})](H{sub 2}O){sub 2}{r_brace}.H{sub 2}O 2, Mn[NH{sub 2}(CH{sub 2}PO{sub 3}H)(CH{sub 2}PO{sub 3})](H{sub 2}O) 3 and {l_brace}Cu{sub 4}[NH(CH{sub 2}PO{sub 3}){sub 2}]{sub 2}(4,4'-bipy)(H{sub 2}O){sub 4}{r_brace}.9H{sub 2}O 4 have been synthesized and structurally characterized. Compound 1 has a linear chain structure, and compound 2 is layered. Compound 3 is three dimensional whereas compound 4 has a pillar-layered structure. Compounds 2 and 3 show predominant antiferromagnetic interactions between magnetic centers.},
doi = {10.1016/j.jssc.2005.10.015},
journal = {Journal of Solid State Chemistry},
number = 1,
volume = 179,
place = {United States},
year = {Sun Jan 15 00:00:00 EST 2006},
month = {Sun Jan 15 00:00:00 EST 2006}
}
  • Five Zn(II) and Cd(II) coordination polymers, [Zn{sub 2}(BOABA)(bpp)(OH)]{center_dot}0.5H{sub 2}O (1), [Cd{sub 3}(BOABA){sub 2}(bpp){sub 2}(H{sub 2}O){sub 6}]{center_dot}2H{sub 2}O (2), [Cd{sub 3}(BOABA){sub 2}(2,2 Prime -bipy){sub 3}(H{sub 2}O){sub 4}]{center_dot}5.5H{sub 2}O (3), [CdNa(BOABA)(H{sub 2}O)]{sub 2}{center_dot}H{sub 2}O (4) and [Cd{sub 2}(BOABA)(bimb)Cl(H{sub 2}O){sub 2}]{center_dot}H{sub 2}O (5) (H{sub 3}BOABA=3,5-bis-oxyacetate-benzoic acid, bpp=1,3-bi(4-pyridyl)propane, 2,2 Prime -bipy=2,2 Prime -bipyridine, bimb=1,4-bis(imidazol-1 Prime -yl)butane), have been solvothermally synthesized and characterized by single-crystal X-ray diffraction, elemental analyses, IR spectra and TG analyses. 1 is an uninodal 4-connected 2D square grid network based on binuclear zinc clusters. 2 is 2D wavelike layer structure and further linked by hydrogen bonds into the final 3D (5,6,6)-connectedmore » topology network. 3 is 3-connected 2D topology network and the 2,2 Prime -bipy ligands decorate in two different types. 4 is a (4,8)-connected 2D topology network with heterocaryotic {l_brace}Cd{sub 2}Na{sub 2}{r_brace} clusters and BOABA{sup 3-} ligands. 5 can be rationalized as a (3,10)-connected 3D topology network with tetranuclear {l_brace}Cd{sub 4}Cl{sub 2}{r_brace} clusters and BOABA{sup 3-} ligands. Meanwhile, photoluminescence studies revealed that these five coordination polymers display strong fluorescent emission bands in the solid state at room temperature. - Graphical abstract: Five new d{sup 10} metal(II) coordination polymers based on H{sub 3}BOABA ligand were obtained and characterized. They display different topological structures and luminescent properties. Highlights: Black-Right-Pointing-Pointer Five d{sup 10} metal(II) polymers based on 3,5-bis-oxyacetate-benzoic acid were obtained. Black-Right-Pointing-Pointer The polymers were structurally characterized by single-crystal X-ray diffraction. Black-Right-Pointing-Pointer Polymers 1-5 display different topological structures. Black-Right-Pointing-Pointer They show strong fluorescent emission bands in the solid state.« less
  • To explore the possibility of obtaining the metal-organic frameworks (MOFs) bearing the bsgluH{sub 2} ligand, two new Cd(II) and one Cu(II) coordination polymers, [Cd(bsglu)(bipy)] {sub n} (1), [Cd(bsglu).(H{sub 2}O)] {sub n} (2) and {l_brace}[Cu{sub 2}(bsglu){sub 2}(bipy){sub 2}].4H{sub 2}O{r_brace} {sub n} (3) (bsglu=N-benzesulfonyl-glutamic acid bianion, bipy=2,2'-bipyridine) were synthesized and characterized by IR, elemental analysis and X-ray diffraction analysis. Compounds 1 and 3 exhibit one-dimensional coordination chains, which are further connected to form two-dimensional supramolecular networks through {pi}-{pi} aromatic stacking interactions in a novel zipper-like way. Compound 2 presents a two-dimensional layer structure. To the best of our knowledge, 2 is themore » first two-dimensional complex formed from transition metal and bsgluH{sub 2} ligand. Interestingly, the bsglu anion exhibits remarkable versatile coordination modes in these complexes. Fluorescent analyses show that 1 exhibits photoluminescence in the solid state. Magnetic measurements for 3 revealed that the Cu(II) chain exhibit a weak antiferromagnetic behavior with a J value of -0.606 cm{sup -1}. - Graphical abstract: Three new complexes, [Cd(bsglu)(bipy)] {sub n} (1), [Cd(bsglu).(H{sub 2}O)] {sub n} (2) and {l_brace}[Cu{sub 2}(bsglu){sub 2}(bipy){sub 2}].4H{sub 2}O{r_brace} {sub n} (3), constructed from Cd(II) or Cu(II) salt with N-benzesulfonyl-glutamic acid were synthesized and characterized. Compounds 1 and 3 exhibit one-dimensional chains which are further connected to form two-dimensional supramolecular networks through {pi}-{pi} aromatic stacking interactions in a novel zipper-like way. Compound 2 presents a two-dimensional layer structure. Luminescence of 1 and magnetic properties of 3 are also investigated.« less
  • In this work, the rod-like ligand 1,4-bis(imidazol-1-yl)-benzene (bib) has been utilized as a building block to perform counterion researches on the structural diversities of coordination polymers. A series of new manganese compounds, ([Mn(bib){sub 3}(ClO{sub 4}){sub 2}](CHCl{sub 3}){sub 2}){sub n} (1), [Mn(bib){sub 2}(N{sub 3}){sub 2}]{sub n} (2), [Mn(bib){sub 2}(HCO{sub 2}){sub 2}]{sub n} (3), [Mn(bib){sub 2}(Ac){sub 2}]{sub n} (4), ([Mn(bib){sub 2}(CF{sub 3}SO{sub 3}){sub 2}](CH{sub 2}Cl{sub 2}){sub 4}){sub n} (5), and [Mn(bib){sub 2}(SO{sub 4})]{sub n} (6) have been successfully synthesized. Compound 1 shows a 3D interpenetrating α-Po network only based on the bib linker. Compounds 2 and 3 exhibit a 2D (4,4) layermore » with parallel and incline interpenetration, respectively. Compounds 4 and 5 display a parallel-packing 2D (4,4) layer with the porosity of 23.4% and 61.4%, respectively. Compound 6 furnishes a 3D α-Po framework with a 2D (4,4) layer pillared by the μ{sub 2}-SO{sub 4}{sup 2−} ion. The structural diversities among 1–6 have been carefully discussed, and the roles of counterions (from coordination affinity and molecular size) in the self-assembly of coordination polymers have also been well documented. Furthermore, magnetic properties of 6 have been carefully studied. - Graphical abstract: Six new compounds have been successfully synthesized. Structural studies reveal that the topology, entanglement and porosity are tunable by the counterion. Furthermore, the weak ferromagnetic coupling is conducted in 6. - Highlights: • Six new Mn{sup II} compounds have been synthesized. • Compounds 1–3 exhibit diverse interpenetrating frameworks. • Compounds 4 and 5 exhibit 3D packing porous architectures. • The tunable effect of counterion has been documented. • Magnetic properties of 6 have been studied by fitting the data.« less
  • Ferromagnetic interactions between imino nitroxides through Diamagnetic Metal Ions: Crystal Structures, Magnetism, and Electronic Properties of [M{sup I}(imino nitroxide){sub 2}](PF{sub 6}) (M = Cu{sup I} and Ag{sup I}) Cu(I) and Ag(I) complexes with imino nitroxides, [Cu{sup I}-(immepy){sub 2}](PF{sub 6}) and [Ag{sup I}(impy){sub 2}](PF{sub 6}), were structurally and magnetically characterized. Magnetic susceptibility and EPR measurements revealed that the magnetic interaction in the Cu(I) complex is ferromagnetic with a J value of 55.1(6) cm{sup -1} (g = 2.0 and H = -JS{sub 1}{center_dot}S{sub 2}), while the Ag(I) complex shows a very weak ferromagnetic interaction. The magnetic behaviors were discussed in terms ofmore » orthogonality of magnetic orbitals and metal to ligand charge-transfer interactions.« less
  • Five novel Zn{sup II}-(pyridyl)imidazole derivative coordination polymers, [Zn(L){sub 2}] (1), [Zn{sub 2}(mu{sub 3}-OH)L(m-BDC)] (2), [Zn{sub 2}(mu{sub 3}-OH)L(p-BDC)].H{sub 2}O (3), [Zn{sub 2}L(BTC)(H{sub 2}O)].2.5H{sub 2}O (4) and [Zn{sub 3.5}(mu{sub 3}-OH)L{sub 2}(BTEC)(H{sub 2}O)].H{sub 2}O (5) (L=4-((2-(pyridine-2-yl)-1H-imidazol-1-yl)methyl)benzoic acid, p-H{sub 2}BDC=1,4-benzenedicarboxylic acid, m-H{sub 2}BDC=1,3-benzenedicarboxylic acid, H{sub 3}BTC=1,3,5-benzenetricarboxylic acid, H{sub 4}BTEC=1,2,4,5-benzenetetracarboxylic acid), were successfully synthesized under hydrothermal conditions through varying auxiliary aromatic-acid ligands and structurally characterized by X-ray crystallography. Compound 1 exhibits a 1D chain linked via double L bridges. Compound 2 features a well-known pcu topology with bent dicarboxylate ligand (m-H{sub 2}BDC) as an auxiliary ligand, while 3 displays a bcu network with linear dicarboxylatemore » ligand (p-H{sub 2}BDC) as an auxiliary ligand. The structure of compound 4 is a novel 3D (3,5)-connected network with (4.6{sup 2})(4.6{sup 4}.8{sup 2}.10.12{sup 2}) topology. It is interesting that compound 5 shows an intricate (3,4,8)-connected framework with (4.6{sup 2})(4{sup 2}.6{sup 3}.8)(4{sup 2}.6{sup 4})(4{sup 2}.6{sup 18}.7.8{sup 6}.10) topology. In addition, their infrared spectra (IR), X-ray powder diffraction (XPRD) and photoluminescent properties were also investigated in detail. - Graphical abstract: Five novel Zn{sup II}-organic architectures have been hydrothermally synthesized through varying auxiliary aromatic-acid ligands and characterized by X-ray diffraction, the photoluminescence properties of compounds 1-5 were studied.« less