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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).
Inorg Chem. 2010 Oct 04; 49(19):9012-25.IC

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.

Authors+Show Affiliations

Department of Chemistry, University of Calcutta, 92 A. P. C. Road, Kolkata 700 009, India.No affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

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

Language

eng

PubMed ID

20812685

Citation

Jana, Arpita, et al. "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)." Inorganic Chemistry, vol. 49, no. 19, 2010, pp. 9012-25.
Jana A, Majumder S, Carrella L, et al. 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). Inorg Chem. 2010;49(19):9012-25.
Jana, A., Majumder, S., Carrella, L., Nayak, M., Weyhermueller, T., Dutta, S., Schollmeyer, D., Rentschler, E., Koner, R., & Mohanta, S. (2010). 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). Inorganic Chemistry, 49(19), 9012-25. https://doi.org/10.1021/ic101445n
Jana A, et al. 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). Inorg Chem. 2010 Oct 4;49(19):9012-25. PubMed PMID: 20812685.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - 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). AU - Jana,Arpita, AU - Majumder,Samit, AU - Carrella,Luca, AU - Nayak,Malabika, AU - Weyhermueller,Thomas, AU - Dutta,Supriya, AU - Schollmeyer,Dieter, AU - Rentschler,Eva, AU - Koner,Rajesh, AU - Mohanta,Sasankasekhar, PY - 2010/9/4/entrez PY - 2010/9/4/pubmed PY - 2011/1/22/medline SP - 9012 EP - 25 JF - Inorganic chemistry JO - Inorg Chem VL - 49 IS - 19 N2 - 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. SN - 1520-510X UR - https://www.unboundmedicine.com/medline/citation/20812685/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__ L2 - https://dx.doi.org/10.1021/ic101445n DB - PRIME DP - Unbound Medicine ER -