Syntheses, Structures, and Magnetic Properties of Diphenoxo-Bridged CuIILnIII and NiII(Low-Spin)LnIII Compounds Derived from a Compartmental Ligand (Ln = Ce-Yb)

Autoren

Arpita Jana
Samit Majumder
Luca Carrella
Malabika Nayak
Thomas Weyhermueller
Supriya Dutta
Dieter Schollmeyer
Eva Rentschler
Rajesh Koner
Sasankasekhar Mohanta

DOI

10.1021/ic101445n

eISSN

1520-510X

ISSN

0020-1669

Ausgabe der Veröffentlichung

19

Zeitschrift

Inorganic Chemistry

Sprache

en

Online publication date

2010

Paginierung

9012 - 9025

Datum der Veröffentlichung

2010

Status

Published

Herausgeber

American Chemical Society (ACS)

Herausgeber URL

http://dx.doi.org/10.1021/ic101445n

Datum der Datenerfassung

2023

Titel

Syntheses, Structures, and Magnetic Properties of Diphenoxo-Bridged CuIILnIII and NiII(Low-Spin)LnIII Compounds Derived from a Compartmental Ligand (Ln = Ce−Yb)

Ausgabe der Zeitschrift

49

Data source: Crossref

Abstract

Syntheses, characterization, and magnetic properties of a series of diphenoxo-bridged discrete dinuclear M(II)Ln(III) complexes (M = Cu or Ni, Ln = Ce-Yb) derived from the compartmental Schiff base ligand, H(2)L, obtained on condensation of 3-ethoxysalicylaldehyde with trans-1,2-diaminocyclohexane, are described. Single crystal X-ray structures of eight Cu(II)Ln(III) compounds (Ln = Ce (1), Pr (2), Nd (3), Sm (4), Tb (7), Ho (9), Er (10), and Yb (12)) and three Ni(II)Ln(III) (Ln = Ce (13), Sm (16), and Gd (18)) compounds have been determined. Considering the previously reported structure of the Cu(II)Gd(III) (6) compound (Eur. J. Inorg. Chem. 2005, 1500), a total of twelve structures are discussed/compared in this study. Four types of composition are observed in the Cu(II)Ln(III) complexes: [Cu(II)LLn(III) (NO(3))(3)(H(2)O)] (1-3: Ln = Ce-Nd), [Cu(II)LSm(III)(NO(3))(3)]·CH(3)COCH(3) (4), [Cu(II)(H(2)O)LLn(III)(NO(3))(3)] (5: Ln = Eu; 6: Ln = Gd), and [Cu(II)LLn(III)(NO(3))(3)] (4A: Ln = Sm; 7-12: Ln = Tb-Yb). On the other hand, the Ni(II)Ln(III) complexes are characterized to have two types of composition: [Ni(II)LLn(III)(H(2)O)(NO(3))(3)] (13-15: Ln = Ce-Nd) and [Ni(II)LLn(III)(NO(3))(3)]·0.5CH(3)COCH(3) (16-24: Ln = Sm-Yb). Among twelve X-ray structures, seven belong to three different isomorphous sets (Cu(II)Ce(III) (1), Cu(II)Pr(III) (2), Cu(II)Nd(III) (3), and Ni(II)Ce(III) (13); Cu(II)Tb(III) (7), Cu(II)Ho(III) (9), Cu(II)Er(III) (10), and Cu(II)Yb(III) (12); Ni(II)Sm(III) (16) and Ni(II)Gd(III) (18)), whereas space group/unit cell parameters of two others (Cu(II)Sm(III) (4) and Cu(II)Gd(III) (6)) are of different types. The lanthanide(III) centers in Cu(II)Ce(III) (1), Cu(II)Pr(III) (2), Cu(II)Nd(III) (3), and Ni(II)Ce(III) (13) complexes are eleven-coordinated, while the lanthanide(III) centers in other compounds are ten-coordinated. As evidenced from the dihedral angle (δ) between the CuO(phenoxo)(2) and LnO(phenoxo)(2) planes, variation in the extent of planarity of the bridging moiety in the Cu(II)Ln(III) compounds takes place; the ranges of δ values are 0.8-6.2° in the 4f(1-7) analogues and 17.6-19.1° in the 4f(8-13) analogues. The Cu(II)Gd(III) (6) compound exhibits ferromagnetic interaction (Eur. J. Inorg. Chem. 2005, 1500). The nature of the magnetic exchange interaction in the Cu(II)Ln(III) complexes has been understood by utilizing the empirical approach; the Ni(II)Ln(III) complexes have been used as references. The metal centers in the Eu(III) complex are uncorrelated, while other 4f(1-6) analogues (Ce(III), Pr(III), Nd(III), and Sm(III)) exhibit antiferromagnetic interaction. Among the higher analogues (4f(7-13)), only Yb(III) exhibits antiferromagnetic interaction, while interaction in other analogues (Gd(III), Tb(III), Dy(III), Ho(III), Er(III), and Tm(III)) is ferromagnetic. An important aspect of the present study is the measurement of the magnetic susceptibility of the unblocked samples as well as on blocking the samples with grease to avoid powder reorientation, if any. Comparison of the two sets of data reveals significant difference in some cases.

Addresses

Department of Chemistry, University of Calcutta, 92 A. P. C. Road, Kolkata 700 009, India.

Autoren

Arpita Jana
Samit Majumder
Luca Carrella
Malabika Nayak
Thomas Weyhermueller
Supriya Dutta
Dieter Schollmeyer
Eva Rentschler
Rajesh Koner
Sasankasekhar Mohanta

DOI

10.1021/ic101445n

eISSN

1520-510X

Externe Identifier

PubMed Identifier: 20812685

Open access

false

ISSN

0020-1669

Ausgabe der Veröffentlichung

19

Zeitschrift

Inorganic chemistry

Schlüsselwörter

Lanthanoid Series Elements
Copper
Nickel
Organometallic Compounds
Ligands
Crystallography, X-Ray
Molecular Structure
Stereoisomerism
Magnetics
Models, Molecular

Sprache

eng

Medium

Print

Paginierung

9012 - 9025

Datum der Veröffentlichung

2010

Status

Published

Datum der Datenerfassung

2010

Titel

Syntheses, structures, and magnetic properties of diphenoxo-bridged Cu(II)Ln(III) and Ni(II)(low-spin)Ln(III) compounds derived from a compartmental ligand (Ln = Ce-Yb).

Sub types

Research Support, Non-U.S. Gov't
Journal Article

Ausgabe der Zeitschrift

49

Data source: Europe PubMed Central

Abstract

Syntheses, characterization, and magnetic properties of a series of diphenoxo-bridged discrete dinuclear M(II)Ln(III) complexes (M = Cu or Ni, Ln = Ce-Yb) derived from the compartmental Schiff base ligand, H(2)L, obtained on condensation of 3-ethoxysalicylaldehyde with trans-1,2-diaminocyclohexane, are described. Single crystal X-ray structures of eight Cu(II)Ln(III) compounds (Ln = Ce (1), Pr (2), Nd (3), Sm (4), Tb (7), Ho (9), Er (10), and Yb (12)) and three Ni(II)Ln(III) (Ln = Ce (13), Sm (16), and Gd (18)) compounds have been determined. Considering the previously reported structure of the Cu(II)Gd(III) (6) compound (Eur. J. Inorg. Chem. 2005, 1500), a total of twelve structures are discussed/compared in this study. Four types of composition are observed in the Cu(II)Ln(III) complexes: [Cu(II)LLn(III) (NO(3))(3)(H(2)O)] (1-3: Ln = Ce-Nd), [Cu(II)LSm(III)(NO(3))(3)]·CH(3)COCH(3) (4), [Cu(II)(H(2)O)LLn(III)(NO(3))(3)] (5: Ln = Eu; 6: Ln = Gd), and [Cu(II)LLn(III)(NO(3))(3)] (4A: Ln = Sm; 7-12: Ln = Tb-Yb). On the other hand, the Ni(II)Ln(III) complexes are characterized to have two types of composition: [Ni(II)LLn(III)(H(2)O)(NO(3))(3)] (13-15: Ln = Ce-Nd) and [Ni(II)LLn(III)(NO(3))(3)]·0.5CH(3)COCH(3) (16-24: Ln = Sm-Yb). Among twelve X-ray structures, seven belong to three different isomorphous sets (Cu(II)Ce(III) (1), Cu(II)Pr(III) (2), Cu(II)Nd(III) (3), and Ni(II)Ce(III) (13); Cu(II)Tb(III) (7), Cu(II)Ho(III) (9), Cu(II)Er(III) (10), and Cu(II)Yb(III) (12); Ni(II)Sm(III) (16) and Ni(II)Gd(III) (18)), whereas space group/unit cell parameters of two others (Cu(II)Sm(III) (4) and Cu(II)Gd(III) (6)) are of different types. The lanthanide(III) centers in Cu(II)Ce(III) (1), Cu(II)Pr(III) (2), Cu(II)Nd(III) (3), and Ni(II)Ce(III) (13) complexes are eleven-coordinated, while the lanthanide(III) centers in other compounds are ten-coordinated. As evidenced from the dihedral angle (δ) between the CuO(phenoxo)(2) and LnO(phenoxo)(2) planes, variation in the extent of planarity of the bridging moiety in the Cu(II)Ln(III) compounds takes place; the ranges of δ values are 0.8-6.2° in the 4f(1-7) analogues and 17.6-19.1° in the 4f(8-13) analogues. The Cu(II)Gd(III) (6) compound exhibits ferromagnetic interaction (Eur. J. Inorg. Chem. 2005, 1500). The nature of the magnetic exchange interaction in the Cu(II)Ln(III) complexes has been understood by utilizing the empirical approach; the Ni(II)Ln(III) complexes have been used as references. The metal centers in the Eu(III) complex are uncorrelated, while other 4f(1-6) analogues (Ce(III), Pr(III), Nd(III), and Sm(III)) exhibit antiferromagnetic interaction. Among the higher analogues (4f(7-13)), only Yb(III) exhibits antiferromagnetic interaction, while interaction in other analogues (Gd(III), Tb(III), Dy(III), Ho(III), Er(III), and Tm(III)) is ferromagnetic. An important aspect of the present study is the measurement of the magnetic susceptibility of the unblocked samples as well as on blocking the samples with grease to avoid powder reorientation, if any. Comparison of the two sets of data reveals significant difference in some cases.

Autoren

Arpita Jana
Samit Majumder
Luca Carrella
Malabika Nayak
Thomas Weyhermueller
Supriya Dutta
Dieter Schollmeyer
Eva Rentschler
Rajesh Koner
Sasankasekhar Mohanta

Autoren-URL

https://www.ncbi.nlm.nih.gov/pubmed/20812685

DOI

10.1021/ic101445n

eISSN

1520-510X

Ausgabe der Veröffentlichung

19

Zeitschrift

Inorg Chem

Schlüsselwörter

Copper
Crystallography, X-Ray
Lanthanoid Series Elements
Ligands
Magnetics
Models, Molecular
Molecular Structure
Nickel
Organometallic Compounds
Stereoisomerism

Sprache

eng

Country

United States

Paginierung

9012 - 9025

Datum der Veröffentlichung

2010

Status

Published

Datum, an dem der Datensatz öffentlich gemacht wurde

2011

Titel

Syntheses, structures, and magnetic properties of diphenoxo-bridged Cu(II)Ln(III) and Ni(II)(low-spin)Ln(III) compounds derived from a compartmental ligand (Ln = Ce-Yb).

Sub types

Journal Article
Research Support, Non-U.S. Gov't

Ausgabe der Zeitschrift

49

Data source: PubMed

Syntheses, Structures, and Magnetic Properties of Diphenoxo-Bridged CuIILnIII and NiII(Low-Spin)LnIII Compounds Derived from a Compartmental Ligand (Ln = Ce-Yb)

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