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Magneto-structural variety of new 3d-4f-4(5)d heterotrimetallic complexes.
Dalton Trans. 2015 Oct 14; 44(38):16713-27.DT

Abstract

Three families of heterotrimetallic chains (type 1-type 3), with different topologies, have been obtained by reacting the 3d-4f complexes, [{Cu(L(1))}xLn(NO3)3] with x = 1 or 2, formed in situ by the reaction of Schiff-base bi-compartmental [Cu(II)(L(1))] complexes and lanthanide(iii) salts, with (NHBu3)3[M(CN)8] (M = Mo(V), W(V)). For type 1 series of compounds, 1-D coordination polymers, with the general formula [{Cu2(valpn)2Ln}{M(CN)8}]·nH2O·mCH3CN (where H2valpn = 1,3-propanediylbis(2-iminomethylene-6-methoxy-phenol), result from the association of trinuclear {CuLn(III)} moieties and [M(V)(CN)8](3-) anions acting as tri-connecting spacers [Ln = La (1), Ce (2), Eu (3), Tb (4), Ho (5), M = Mo; Ln = Tb (6), Ho (7), M = W; m = 0, n = 1.5 (7) and 2 (1-4, 6); n = 1, m = 1 (5)]. The type 2 family has the general formula [{Cu(valdp)Ln(H2O)4}{M(CN)8}]·2H2O·CH3CN (where H2valdp = 1,2-propanediylbis(2-iminomethylene-6-methoxy-phenol)) and also consists of heterotrimetallic chains involving binuclear {Cu(II)Ln(III)} units linked to [M(CN)8](3-) anions coordinating through two cyano groups [Ln = Gd (8), Tb (9), Dy (10); M = Mo; Ln = La (11), Gd (12), Tb (13), Dy (14); M = W]. With large Ln(III) ions (La(III) and Pr(III)), the type 3 family of heterotrimetallic compounds are assembled: [{Cu2(valdp)2Ln(H2O)4}{Mo(CN)8}]·nCH3OH·mCH3CN, n, m = 0, Ln = La (15); n = m = 1, Pr (16), in which the trinuclear {CuLn(III)} nodes are connected to [Mo(V)(CN)8](3-) anions that act as tetra-connecting spacers. For Tb(III) derivatives of the type 1 (compounds 4 and 6), the DC magnetic properties indicate a predominant ferromagnetic Cu(II)-Tb(III) interaction, while the AC magnetic susceptibility (in the presence of a static magnetic field, HDC = 3000 Oe) emphasize the slow relaxation of the magnetization (Ueff/kB = 20.55 K and τ0 = 5.5 × 10(-7) s for compound 4, Ueff/kBT = 15.1 K and τ0 = 1.5 × 10(-7) s for compound 6). A predominant ferromagnetic Cu(II)-Ln(III) interaction was also observed in the type 2 series (compounds 8-10 and 12-14) as a result of the magnetic coupling between copper(ii) and lanthanide(iii) ions via the phenoxo-bridge. The magnetic behavior for the La(III) derivatives reveals that weak ferromagnetic interactions are also operative between the Cu(II) and the 4d/5d centers.

Authors+Show Affiliations

Coordination and Supramolecular Chemistry Laboratory, Institute of Physical Chemistry "Ilie Murgulescu" Romanian Academy, Splaiul Independentei 202, 060021 Bucharest, Romania. diana.visinescu@gmail.com.No affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info availableNo affiliation info available

Pub Type(s)

Journal Article

Language

eng

PubMed ID

26199073

Citation

Visinescu, Diana, et al. "Magneto-structural Variety of New 3d-4f-4(5)d Heterotrimetallic Complexes." Dalton Transactions (Cambridge, England : 2003), vol. 44, no. 38, 2015, pp. 16713-27.
Visinescu D, Alexandru MG, Madalan AM, et al. Magneto-structural variety of new 3d-4f-4(5)d heterotrimetallic complexes. Dalton Trans. 2015;44(38):16713-27.
Visinescu, D., Alexandru, M. G., Madalan, A. M., Pichon, C., Duhayon, C., Sutter, J. P., & Andruh, M. (2015). Magneto-structural variety of new 3d-4f-4(5)d heterotrimetallic complexes. Dalton Transactions (Cambridge, England : 2003), 44(38), 16713-27. https://doi.org/10.1039/c5dt01738f
Visinescu D, et al. Magneto-structural Variety of New 3d-4f-4(5)d Heterotrimetallic Complexes. Dalton Trans. 2015 Oct 14;44(38):16713-27. PubMed PMID: 26199073.
* Article titles in AMA citation format should be in sentence-case
TY - JOUR T1 - Magneto-structural variety of new 3d-4f-4(5)d heterotrimetallic complexes. AU - Visinescu,Diana, AU - Alexandru,Maria-Gabriela, AU - Madalan,Augustin M, AU - Pichon,Céline, AU - Duhayon,Carine, AU - Sutter,Jean-Pascal, AU - Andruh,Marius, Y1 - 2015/07/22/ PY - 2015/7/23/entrez PY - 2015/7/23/pubmed PY - 2015/7/23/medline SP - 16713 EP - 27 JF - Dalton transactions (Cambridge, England : 2003) JO - Dalton Trans VL - 44 IS - 38 N2 - Three families of heterotrimetallic chains (type 1-type 3), with different topologies, have been obtained by reacting the 3d-4f complexes, [{Cu(L(1))}xLn(NO3)3] with x = 1 or 2, formed in situ by the reaction of Schiff-base bi-compartmental [Cu(II)(L(1))] complexes and lanthanide(iii) salts, with (NHBu3)3[M(CN)8] (M = Mo(V), W(V)). For type 1 series of compounds, 1-D coordination polymers, with the general formula [{Cu2(valpn)2Ln}{M(CN)8}]·nH2O·mCH3CN (where H2valpn = 1,3-propanediylbis(2-iminomethylene-6-methoxy-phenol), result from the association of trinuclear {CuLn(III)} moieties and [M(V)(CN)8](3-) anions acting as tri-connecting spacers [Ln = La (1), Ce (2), Eu (3), Tb (4), Ho (5), M = Mo; Ln = Tb (6), Ho (7), M = W; m = 0, n = 1.5 (7) and 2 (1-4, 6); n = 1, m = 1 (5)]. The type 2 family has the general formula [{Cu(valdp)Ln(H2O)4}{M(CN)8}]·2H2O·CH3CN (where H2valdp = 1,2-propanediylbis(2-iminomethylene-6-methoxy-phenol)) and also consists of heterotrimetallic chains involving binuclear {Cu(II)Ln(III)} units linked to [M(CN)8](3-) anions coordinating through two cyano groups [Ln = Gd (8), Tb (9), Dy (10); M = Mo; Ln = La (11), Gd (12), Tb (13), Dy (14); M = W]. With large Ln(III) ions (La(III) and Pr(III)), the type 3 family of heterotrimetallic compounds are assembled: [{Cu2(valdp)2Ln(H2O)4}{Mo(CN)8}]·nCH3OH·mCH3CN, n, m = 0, Ln = La (15); n = m = 1, Pr (16), in which the trinuclear {CuLn(III)} nodes are connected to [Mo(V)(CN)8](3-) anions that act as tetra-connecting spacers. For Tb(III) derivatives of the type 1 (compounds 4 and 6), the DC magnetic properties indicate a predominant ferromagnetic Cu(II)-Tb(III) interaction, while the AC magnetic susceptibility (in the presence of a static magnetic field, HDC = 3000 Oe) emphasize the slow relaxation of the magnetization (Ueff/kB = 20.55 K and τ0 = 5.5 × 10(-7) s for compound 4, Ueff/kBT = 15.1 K and τ0 = 1.5 × 10(-7) s for compound 6). A predominant ferromagnetic Cu(II)-Ln(III) interaction was also observed in the type 2 series (compounds 8-10 and 12-14) as a result of the magnetic coupling between copper(ii) and lanthanide(iii) ions via the phenoxo-bridge. The magnetic behavior for the La(III) derivatives reveals that weak ferromagnetic interactions are also operative between the Cu(II) and the 4d/5d centers. SN - 1477-9234 UR - https://www.unboundmedicine.com/medline/citation/26199073/Magneto_structural_variety_of_new_3d_4f_4_5_d_heterotrimetallic_complexes_ L2 - https://doi.org/10.1039/c5dt01738f DB - PRIME DP - Unbound Medicine ER -
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