Magnetic, thermal and spectroscopic properties of lanthanide(III) 2-(4-chlorophenoxy) acetates, Ln(C8H6ClO3)3•nH2O

4-Chlorophenoxyacetates of lanthanides(III) were synthesized as polycrystalline hydrated solids with the general formulae: Ln(C8H6ClO3)3?2H2O (Ln = La(III), Pr(III), Sm(III), Eu(III) and Tb(III)), Ln(C8H6ClO3)3?H2O (Ln = Dy(III)) and Ln(C8H6ClO3)3?3H2O (Ln = Er(III), Tm(III), Yb(III) and Lu(III) and characterized by elemental analysis, FTIR spectroscopy, magnetic and thermogravimetric studies and also by X-ray diffraction (XRD) measurements. The complexes have colours typical for lanthanide(III) ions. The carboxylate groups bind as bidentate chelating. On heating to 1273 K in air the complexes decompose in three steps. At first they dehydrate in one stage to form anhydrous salts that next decompose to the oxides of respective metals with the intermediate formation of their oxychlorides. The gaseous products of compound thermal decomposition in nitrogen were also determined and the magnetic susceptibilities were measured over the ranges 76-303K and 1.8-303K, and their magnetic moments were calculated. The results show that 4-chlorophenoxyacetates of lanthanides(III) are high-spin complexes with weak ligand field.

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Complexes of Light Lanthanides with 3,4-Dimethoxybenzoic Acid

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc20000179 ◽

2000 ◽

Vol 65 (2) ◽

pp. 179-191 ◽

Cited By ~ 8

Author(s):

Wiesława Ferenc ◽

Agnieszka Walków-Dziewulska

Keyword(s):

Magnetic Moments ◽

Intermediate Formation ◽

Lanthanide Ions ◽

Ligand Field ◽

X Ray Diffraction ◽

Magnetic Studies ◽

X Ray ◽

Light Lanthanides ◽

Polycrystalline Solids ◽

Van Vleck

The complexes of light lanthanides with 3,4-dimethoxybenzoic acid, Ln(C9H9O4)3·4 H2O, where Ln = La(III), Ce(III), Pr(III), Nd(III), Sm(III), Eu(III) and Gd(III), have been synthesized as polycrystalline solids and characterized by elemental analysis, IR spectroscopy, thermogravimetric and magnetic studies and X-ray diffraction measurements. The complexes possess colours typical of Ln(III) ions (La, Ce, Eu, Gd white, Pr greenish, Nd violet and Sm cream). The carboxylate group in these complexes binds as a symmetrical, bidentate chelating ligand. On heating in air to 1 273 K the 3,4-dimethoxybenzoates of Ce(III), Pr(III), Sm(III), Eu(III) and Gd(III) first dehydrate to anhydrous salts that further decompose to oxides of the respective metals. The 3,4-dimethoxybenzoates of La(III) and Nd(III) decompose in three steps. Firstly, they dehydrate to anhydrous salts that further decompose to the oxides with the intermediate formation of oxycarbonates. The solubilities of the studied complexes in water at 293 K is in the order of 10-4-10-3 mol dm-3. Their magnetic moments were determined in the temperature range 77-298 K and found to obey the Curie-Weiss law. The values of μeff calculated for the all compounds (except that for Eu) are close to those obtained for Ln(III) by Hund and van Vleck. The results show that there is no influence of the ligand field on 4f electrons of the lanthanide ions in these polycrystalline compounds; 4f electrons probably do not participate in the formation of the Ln-O bonds.

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New Coordination Polymers of Selected Lanthanides with 1,2-Phenylenediacetate Linker: Structures, Thermal and Luminescence Properties

Materials ◽

10.3390/ma14174871 ◽

2021 ◽

Vol 14 (17) ◽

pp. 4871

Author(s):

Renata Łyszczek ◽

Iwona Rusinek ◽

Agnieszka Ostasz ◽

Justyna Sienkiewicz-Gromiuk ◽

Dmytro Vlasyuk ◽

...

Keyword(s):

Single Crystal ◽

Coordination Polymers ◽

Structural Similarity ◽

Spectroscopic Properties ◽

Luminescence Spectroscopy ◽

X Ray Diffraction ◽

Metal Centers ◽

X Ray ◽

Gaseous Products ◽

Carboxylate Groups

Solvothermal reactions of lanthanide (III) salts with 1,2-phenylenediacetic acid in N,N′-dimethylformamide (DMF) solvent lead to the formation of the metal complexes of the general formula Ln2(1,2-pda)3(DMF)2, where Ln(III) = Pr(1), Sm(2), Eu(3), Tb(4), Dy(5), and Er(6), 1,2-pda = [C6H4(CH2COO)2]2−. The compounds were characterized by elemental analysis, powder and single-crystal X-ray diffraction methods, thermal analysis methods (TG-DSC and TG-FTIR), infrared and luminescence spectroscopy. They exhibit structural similarity in the two groups (Pr, Sm, and Eu; Tb, Dy, and Er), which was reflected in their thermal behaviours and spectroscopic properties. Single-crystal X-ray diffraction studies reveal that Sm(2) and Eu(3) complexes form 2D coordination polymers with four crystallographically independent metal centers. Every second lanthanide ion is additionally coordinated by two DMF molecules. The 1,2-phenylenediacetate linker shows different denticity being: penta- and hexadentate while carboxylate groups exhibit bidentate-bridging, bidentate-chelating, and three-dentate bridging-chelating modes. The infrared spectra reflect divergence between these two groups of complexes. The complexes of lighter lanthanides contain in the structure coordinated DMF molecules, while in the structures of heavier complexes, DMF molecules appear in the inner and outer coordination sphere. Both carboxylate groups are deprotonated and engaged in the coordination of metal centers but in different ways in such groups of complexes. In the groups, the thermal decomposition of the isostructural complexes occurs similarly. Pyrolysis of complexes takes place with the formation of such gaseous products as DMF, carbon oxides, ortho-xylene, ethers, water, carboxylic acids, and esters. The complexes of Eu and Tb exhibit characteristic luminescence in the VIS region, while the erbium complex emits NIR wavelength.

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Complexes of 4-chlorophenoxyacetates of Nd(III), Gd(III) and Ho(III)

Eclética Química Journal ◽

10.26850/1678-4618eqj.v35.1.2010.p67-75 ◽

2018 ◽

Vol 35 (1) ◽

pp. 67

Author(s):

W. Ferenc ◽

M. Bernat ◽

J. Sarzyński ◽

H. Głuchowska

Keyword(s):

Thermal Decomposition ◽

Magnetic Moments ◽

X Ray Diffraction ◽

Magnetic Studies ◽

Bridging Ligands ◽

X Ray ◽

Gaseous Products ◽

Carboxylate Groups ◽

One Step ◽

Ligand Fields

The complexes of 4-chlorophenoxyacetates of Nd(III), Gd(III) and Ho(III) have been synthesized as polycrystalline hydrated solids, and characterized by elemental analysis, spectroscopy, magnetic studies and also by X-ray diffraction and thermogravimetric measurements. The analysed complexes have the following colours: violet for Nd(III), white for Gd(III) and cream for Ho(III) compounds. The carboxylate groups bind as bidentate chelating (Ho) or bridging ligands (Nd, Gd). On heating to 1173K in air the complexes decompose in several steps. At first, they dehydrate in one step to form anhydrous salts, that next decompose to the oxides of respective metals. The gaseous products of their thermal decomposition in nitrogen were also determined and the magnetic susceptibilites were measured over the temperature range of 76-303K and the magnetic moments were calculated. The results show that 4-chlorophenoxyacetates of Nd(III), Gd(III) and Ho(III) are high-spin complexes with weak ligand fields. The solubility value in water at 293K for analysed 4-chlorophenoxyacetates is in the order of 10-4mol/dm3.

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Physicochemical properties of 3, 4, 5–trimethoxybenzoates of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II)

Journal of the Serbian Chemical Society ◽

10.2298/jsc0509075f ◽

2005 ◽

Vol 70 (8-9) ◽

pp. 1075-1088 ◽

Cited By ~ 1

Author(s):

Wieslawa Ferenc ◽

Agnieszka Walków-Dziewulska ◽

Jan Sarzynski

Keyword(s):

Ir Spectroscopy ◽

Magnetic Moments ◽

X Ray Diffraction ◽

Acid Anion ◽

Magnetic Studies ◽

Bridging Ligands ◽

Magnetic Susceptibilities ◽

X Ray ◽

Carboxylate Groups ◽

One Step

The complexes of Mn(II), Co(II), Ni(II), Cu(II) and Zn(II) with 3,4,5-trimethoxybenzoic acid anion of the formula: M(C10H11O5)2.nH2O, where n = 6 for Ni(II), n = 1 for Mn(II), Co(II), Cu(II), and n = 0 for Zn, have been synthesized and characterized by elemental analysis, IR spectroscopy X?ray diffraction measurements, thermogravimetry and magnetic studies. They are crystalline compounds characterized by various symmetry. They decompose in various ways when heated in air to 1273 K. At first, they dehydrate in one step and form anhydrous salts. The final products of decomposition are oxides of the respective metals (Mn2O3, Co3O4, NiO, CuO, ZnO). The solubilities of the analysed complexes in water at 293 K are in the orders of 10-2 ? 10-4 mol dm-3. The magnetic susceptibilities of the Mn(II), Co(II), Ni(II) and Cu(II) complexes were measured over the range of 76?303 K and the magnetic moments were calculated. The results show that the 3,4,5-trimethoxybenzoates of Mn(II), Co(II) and Ni(II) are high-spin complexes but that of Cu(II) forms a dimer [Cu2(C10H11O5)4(H2O)2]. The carboxylate groups bind as monodentate or bidentate chelating or bridging ligands.

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Complexes of light lanthanides with 2,4-dimethoxybenzoic acid

Journal of the Serbian Chemical Society ◽

10.2298/jsc0001027f ◽

2000 ◽

Vol 65 (1) ◽

pp. 27-35 ◽

Cited By ~ 4

Author(s):

Wieslawa Ferenc ◽

Agnieszka Walków-Dziewulska

Keyword(s):

Ir Spectroscopy ◽

Intermediate Formation ◽

Carboxylate Group ◽

X Ray Diffraction ◽

X Ray ◽

One Step ◽

Light Lanthanides ◽

Thermogravimetric Studies ◽

Hydrated Complexes ◽

Two Stages

The complexes of light lanthanides with 2,4-dimethoxybenzoic acid of the formula: Ln(C9H9O4)3.nH2O where Ln = La(III), Ce(III), Pr(III), Nd(III), Sm(III), Eu(III), Gd(IIII), and n = 3 for La(III), Gd(III), n = 2 for Sm(III), Eu(III), and n = 0 for Ce(III), Pr(III), Nd(III) have been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric studies and X-ray diffraction measurements. The complexes have colours typical for Ln 3+ ions (La, Ce, Eu, Gd-white, Sm-cream, Pr-green, Nd-violet). The carboxylate group in these complexes is a symmetrical, bidentate, chelating ligand. They are crystalline compounds characterized by various symmetry. On heating in air to 1273 K the 2,4-dimethoxybenzoates of the light lanthanides decompose in various ways. The hydrated complexes decompose in two or three steps while those of anhydrous ones only in one or two. The trihydrate of lanthanum 2,4-dimethoxybenzoate first dehydrates to form the anhydrous salt, which then decomposes to La2O3 via the intermediate formation of La2O2CO3. The hydrates of Sm(III), Eu(III), Gd(III) decompose in two stages. First, they dehydrate forming the anhydrous salts, which then decompose directly to the oxides of the respective metals. The anhydrous complexes of Ce(III), Pr(III) decompose in one step, while that of Nd(III) in two. The solubilities of the 2,4-dimethoxybenzoates of the light lanthanides in water and ethanol at 293 K are in the order of: 10 -3 mol dm -3 and 10 -4.10 -3 mol dm-3, respectively.

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Spectral, thermal and magnetic characterization of 2, 3-dimethoxybenzoates of Co(II), Ni(II) and Cu(II)

Journal of the Serbian Chemical Society ◽

10.2298/jsc0506833f ◽

2005 ◽

Vol 70 (6) ◽

pp. 833-842 ◽

Cited By ~ 6

Author(s):

Wieslawa Ferenc ◽

Agnieszka Walkow-Dziewulska ◽

Pawel Sadowsk ◽

Janusz Chrusciel

Keyword(s):

Magnetic Moments ◽

Electronic Spectroscopy ◽

X Ray Diffraction ◽

Magnetic Studies ◽

Thermal Stabilities ◽

Bridging Ligands ◽

X Ray ◽

Carboxylate Groups ◽

Polycrystalline Solids

Complexes of 2,3-dimethoxybenzoates of Co(II), Ni(II) and Cu(II) have been synthesized as hydrated or anhydrous polycrystalline solids and characterized by elemental analysis, IR, FIR and electronic spectroscopy, magnetic studies and X-ray diffraction measurements. The carboxylate groups bind as monodentate or symmetrical, bidentate chelating and bridging ligands. The thermal stabilities were determined in air. When heated they dehydrate to form anhydrous salts which are decomposed to the oxides of the respective metals. The magnetic susceptibilities of the complexes were measured over the range 77?300 K and the magnetic moments were calculated. The results show that the complexes of Ni(II) and Co(II) are high-spin complexes and that of Cu(II) forms a dimer.

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Complexes of light lanthanides with 2,3-dimethoxybenzoic acid

Journal of the Serbian Chemical Society ◽

10.2298/jsc0108543f ◽

2001 ◽

Vol 66 (8) ◽

pp. 543-553 ◽

Cited By ~ 11

Author(s):

Wieslawa Ferenc ◽

Agnieszka Walków-Dziewulska

Keyword(s):

Ir Spectroscopy ◽

Elemental Analysis ◽

Magnetic Measurements ◽

Magnetic Moments ◽

Intermediate Formation ◽

Carboxylate Group ◽

X Ray ◽

Light Lanthanides ◽

Thermogravimetric Studies ◽

Low Symmetry

The complexes of light lanthanides with 2,3-dimethoxybenzoic acid of the formula: Ln(C9H9O4)3, where Ln = La(III), Ce(III), Pr(III), Nd(III), Sm(III), Eu(III) and Gd(III) have been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric studies, as well as X-ray and magnetic measurements. The complexes have colours typical for Ln3+ ions (La, Ce, Eu, Gd-white, Sm-cream, Pr-green, Nd-violet). The carboxylate group in these complexes is a bidentate, chelating ligand or a tridentate chelating and bridging one. They are crystalline compounds characterized by low symmetry. On heating in air to 1173 K, the 2,3-dimethoxybenzoates of the light lanthanides decompose in various ways. The complexes of Ce(III), Pr(III), Sm(III), Eu(III) and Gd(III) decompose directly to oxides of the respective metals while those of La(III) and Nd(III) via the intermediate formation of La2O2CO3 and Nd2O2CO3. The solubilities of the 2,3-dimethoxybenzoates of the light lanthanides in water at 293Kare in the orders of 10-3-10-2 mol dm-3. The magnetic moments were determined in the range 4.2-298 K and the complexes are found to obey the Curie-Weiss law.

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The physico-chemical properties of 2-methoxyphenoxyacetates of Mn(II), Co(II), Ni(II) and Cu(II)

Eclética Química Journal ◽

10.26850/1678-4618eqj.v35.2.2010.p89-98 ◽

2018 ◽

Vol 35 (2) ◽

pp. 89

Author(s):

W. Ferenc ◽

M. Bernat ◽

J. Sarzyński

Keyword(s):

Magnetic Moments ◽

Chemical Properties ◽

Intermediate Formation ◽

Bidentate Ligands ◽

X Ray Diffraction ◽

Solubility In Water ◽

Physico Chemical ◽

One Step ◽

Thermogravimetric Studies ◽

Ligand Fields

The complexes of 2-methoxyhenoxyacetates of Mn(II), Co(II), Ni(II) and Cu(II)with the general formula: M(C9H9O4)3·4H2O, where M(II) = Mn, Co, Ni and Cu have been synthesized and characterized by elemental analysis, IR spectroscopy, magnetic and thermogravimetric studies and also X-ray diffraction measurements. The complexes have colours typical for M(II) ions (Mn(II) - a pale pink, Co(II) - pink, Ni(II) - green, and Cu(II) – blue). The carboxylate group binds as monodentate and bidentate ligands. On heating to 1273K in air thecomplexes decompose in the same way. At first, they dehydrate in one step to anhydrous salts, that next decompose to the oxides of respective metals with the intermediate formation of the oxycarbonates. Their solubility in water at 293K is of the order of 10-5 mol·dm-3. The magnetic moments of analysed complexes were determined in the range of 76-303K. The results reveal them to be high-spin complexes of weak ligand fields.

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Syntheses, Solid-state Structures and Catalytic Activity of Zinc Carboxylate Complexes in Lactide Polymerization

Zeitschrift für Naturforschung B ◽

10.5560/znb.2014-4133 ◽

2014 ◽

Vol 69 (11-12) ◽

pp. 1365-1374 ◽

Cited By ~ 6

Author(s):

Christoph Scheiper ◽

Christoph Wölper ◽

Dieter Bläser ◽

Joachim Roll ◽

Stephan Schulz

Keyword(s):

Ring Opening ◽

Zinc Complex ◽

X Ray Diffraction ◽

Polymerization Catalysts ◽

Co Catalyst ◽

Carboxylate Complexes ◽

X Ray ◽

Carboxylate Groups ◽

Solid State Structures ◽

Lactide Polymerization

Abstract Three dinuclear zinc carboxylate complexes [L1-3Zn(μ,η2-O2CPh)]2 (1, 2, 4) containing either the bidentate N,N′-chelating β-diketiminate ligand RNC(Me)C(H)C(Me)NR (R = 2,6-iPr2-C6H3, L1, complex 1), the tridentate O,N,N-chelating ligand OC(Me)C(H)C(Me)NCH2CH2NMe2 (L2, complex 2) or the bis-N,N′-chelating bis-β-diketiminate ligand RNC(Me)C(H)C(Me)NNC(Me)- C(H)C(Me)NR (R = 2,6-iPr2-C6H3, L3, complex 4) were synthesized and characterized including single-crystal X-ray diffraction. Reaction of the neutral bis-β-diketimine (L3(H)2) with two equivalents of ZnMe2 leads to the expected heteroleptic dinuclear zinc complex L3(ZnMe)2 3 in 93% yield. Further reaction with benzoic acid PhCO2H leads to complex 4. Complex 2 forms a rather strong carboxylate-bridged dimer, whereas the carboxylate groups in complexes 1 and 4 act as asymmetrical bridges between both Zn atoms, pointing to the formation of a weakly bonded dimer. The zinc atoms in 1 and 4 are tetrahedrally coordinated, whereas in 2 the coordination number is increased to five due to the coordination of the pendant donor arm. The ring opening polymerization (ROP) of rac-lactide was investigated with the zinc complexes 1-4 and diazabicycloundec-7-ene (DBU) as a co-catalyst. Complexes 2 and 3 are active polymerization catalysts, which in the presence of DBU converted 200 equiv. of rac-lactide into polylactide within 10 min at ambient temperature. The analysis of the crude polymer showed that the lactide polymerization with catalyst 2 occurs via a slightly modified activated-monomer mechanism.

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A new twofold interpenetrated two-dimensional cadmium(II) coordination polymer constructed from 2,2′-(benzene-1,4-dicarboxamido)dipropionate

Acta Crystallographica Section C Structural Chemistry ◽

10.1107/s2053229618013967 ◽

2018 ◽

Vol 74 (11) ◽

pp. 1434-1439

Author(s):

Hong-Tao Zhang ◽

Xiao-Long Wang

Keyword(s):

Coordination Polymer ◽

Coordination Polymers ◽

Self Assembly ◽

Fluorescence Emission ◽

Functional Materials ◽

Two Dimensional ◽

X Ray Diffraction ◽

X Ray ◽

Carboxylate Groups ◽

Potential Applications

In recent years, much initial interest and enthusiasm has focused on the self-assembly of coordination polymers due to the aesthetics of their crystalline architectures and their potential applications as new functional materials. As part of an exploration of chiral coordination polymers, a new twofold interpenetrated two-dimensional (2D) coordination polymer, namely, poly[[tetraaquabis[μ3-(2R,2′R)-2,2′-(benzene-1,4-dicarboxamido)dipropionato-κ5 O,O′:O′′,O′′′:O′′]dicadmium(II)] trihydrate], {[Cd2(C14H14N2O6)2(H2O)4]·3H2O} n , has been synthesized by the reaction of Cd(CH3COO)2·2H2O with the designed ligand (2R,2′R)-2,2′-(benzene-1,4-dicarboxamido)dipropionic acid (H2 L). The compound has been structurally characterized by elemental analysis, IR spectroscopy, powder X-ray diffraction and single-crystal X-ray diffraction analysis. In the crystal structure, each CdII cation binds to three carboxylate groups from two crystallographically independent L 2− dianions. Four carboxylate groups link two crystallographically independent cadmium cations into a 4,4-connected secondary building unit (SBU). The resulting SBUs are extended into a two-dimensional folding sheet via the terephthalamide moiety of the ligand as a spacer, which can be simplified as a (4,4)-connected 4,4L15 net with the point symbol (3.53.62)(32.52.62). In the lattice, two independent folding sheets interpenetrate each other to yield a double-sheet layer. The resulting 2D layers pack in parallel arrays through intermolecular hydrogen bonds and interlayer π–π interactions. The thermal stability and photoluminescence properties of the title compound have been investigated and it exhibits an enhanced fluorescence emission and a longer lifetime compared with free H2 L.

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