Assembling Novel Heterotrimetallic Cu/Co/Ni and Cu/Co/Cd Cores Supported by Diethanolamine Ligand in One-Pot Reactions of Zerovalent Copper with Metal Salts

D. Nesterov, V.G. Makhankova, O.Y. Vassilyeva, V.N. Kokozay, L. Kovbasyuk, Brian Skelton, J. Jezierska

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Abstract

The three novel heterotrimetallic complexes [Ni(H2L)(2)][CoCu(L)(2)((HL)-L-2)(NCS)(2)(NCS)(2) (1), [Ni(H2L)(2)][CuCo(L)(2)(H2L)(NCS)](2)Br-2.2H(2)O (2), and [CuCoCd(H2L)(2)(L)(2)(NCS)Br-2]-CH3OH (3) have been prepared using zerovalent copper; cobalt thiocyanate; nickel thiocyanate (1), nickel bromide (2), or cadmium bromide (3); and methanol solutions of diethanolamine in air. The most prominent feature of the structures of 1 and 2 is the formation of the "pentanuclear" aggregate {[Ni(H2L)(2)][CoCu(L)(2)(H2L)(NCS)]2}(2+) made up of two neutral [CoCu(L)(2)(H2L)(NCS)] units and the previously unknown cation [Ni(H2L)(2)](2+) "glued together" by strong complementary hydrogen bonds. With Cd2+ instead of Ni2+, a different structure is obtained: the [CoCu(L)(2)(H2L)(NCS)] unit is now linked to the Cd center through coordination of the oxygens of L groups on the Co atom to form the discrete heterotrimetallic molecular species 3. Cryomagnetic measurements of the compounds show that, in all cases, the magnetic behavior is paramagnetic; the polycrystalline EPR spectra contain signals due to monomeric copper species only. At the same time, the EPR spectra of frozen DMF and methanol solutions of 1-3 reveal the presence of triplet-state species that can be generated only by a coupling of the CU2+ centers within a dimer. The species responsible for the appearance of transitions within the triplet state are thought to be Cu(II) dimeric centers formed by aggregation of two {CuCo(H2L)(L)(2)} fragments of 1-3 present in solution. The residual monomeric spectra in the g approximate to 2 region are indicative of the existence of an equilibrium in solution between the dimeric and monomeric Cu(II) centers in aggregated and free {CuCo(H2L)(L)(2)} fragments, respectively, with varying degrees of stability. The fragmentation process of 1-3 in solution was screened by electrospray ionization mass spectrometry.
Original languageEnglish
Pages (from-to)7868-7876
JournalInorganic Chemistry
Volume43
Issue number9
DOIs
Publication statusPublished - 2004

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diethanolamine
assembling
Copper
Salts
Metals
Ligands
salts
copper
ligands
metals
Bromides
atomic energy levels
Paramagnetic resonance
Methanol
bromides
methyl alcohol
fragments
nickel
Electrospray ionization
Nickel

Cite this

Nesterov, D. ; Makhankova, V.G. ; Vassilyeva, O.Y. ; Kokozay, V.N. ; Kovbasyuk, L. ; Skelton, Brian ; Jezierska, J. / Assembling Novel Heterotrimetallic Cu/Co/Ni and Cu/Co/Cd Cores Supported by Diethanolamine Ligand in One-Pot Reactions of Zerovalent Copper with Metal Salts. In: Inorganic Chemistry. 2004 ; Vol. 43, No. 9. pp. 7868-7876.
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title = "Assembling Novel Heterotrimetallic Cu/Co/Ni and Cu/Co/Cd Cores Supported by Diethanolamine Ligand in One-Pot Reactions of Zerovalent Copper with Metal Salts",
abstract = "The three novel heterotrimetallic complexes [Ni(H2L)(2)][CoCu(L)(2)((HL)-L-2)(NCS)(2)(NCS)(2) (1), [Ni(H2L)(2)][CuCo(L)(2)(H2L)(NCS)](2)Br-2.2H(2)O (2), and [CuCoCd(H2L)(2)(L)(2)(NCS)Br-2]-CH3OH (3) have been prepared using zerovalent copper; cobalt thiocyanate; nickel thiocyanate (1), nickel bromide (2), or cadmium bromide (3); and methanol solutions of diethanolamine in air. The most prominent feature of the structures of 1 and 2 is the formation of the {"}pentanuclear{"} aggregate {[Ni(H2L)(2)][CoCu(L)(2)(H2L)(NCS)]2}(2+) made up of two neutral [CoCu(L)(2)(H2L)(NCS)] units and the previously unknown cation [Ni(H2L)(2)](2+) {"}glued together{"} by strong complementary hydrogen bonds. With Cd2+ instead of Ni2+, a different structure is obtained: the [CoCu(L)(2)(H2L)(NCS)] unit is now linked to the Cd center through coordination of the oxygens of L groups on the Co atom to form the discrete heterotrimetallic molecular species 3. Cryomagnetic measurements of the compounds show that, in all cases, the magnetic behavior is paramagnetic; the polycrystalline EPR spectra contain signals due to monomeric copper species only. At the same time, the EPR spectra of frozen DMF and methanol solutions of 1-3 reveal the presence of triplet-state species that can be generated only by a coupling of the CU2+ centers within a dimer. The species responsible for the appearance of transitions within the triplet state are thought to be Cu(II) dimeric centers formed by aggregation of two {CuCo(H2L)(L)(2)} fragments of 1-3 present in solution. The residual monomeric spectra in the g approximate to 2 region are indicative of the existence of an equilibrium in solution between the dimeric and monomeric Cu(II) centers in aggregated and free {CuCo(H2L)(L)(2)} fragments, respectively, with varying degrees of stability. The fragmentation process of 1-3 in solution was screened by electrospray ionization mass spectrometry.",
author = "D. Nesterov and V.G. Makhankova and O.Y. Vassilyeva and V.N. Kokozay and L. Kovbasyuk and Brian Skelton and J. Jezierska",
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}

Assembling Novel Heterotrimetallic Cu/Co/Ni and Cu/Co/Cd Cores Supported by Diethanolamine Ligand in One-Pot Reactions of Zerovalent Copper with Metal Salts. / Nesterov, D.; Makhankova, V.G.; Vassilyeva, O.Y.; Kokozay, V.N.; Kovbasyuk, L.; Skelton, Brian; Jezierska, J.

In: Inorganic Chemistry, Vol. 43, No. 9, 2004, p. 7868-7876.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Assembling Novel Heterotrimetallic Cu/Co/Ni and Cu/Co/Cd Cores Supported by Diethanolamine Ligand in One-Pot Reactions of Zerovalent Copper with Metal Salts

AU - Nesterov, D.

AU - Makhankova, V.G.

AU - Vassilyeva, O.Y.

AU - Kokozay, V.N.

AU - Kovbasyuk, L.

AU - Skelton, Brian

AU - Jezierska, J.

PY - 2004

Y1 - 2004

N2 - The three novel heterotrimetallic complexes [Ni(H2L)(2)][CoCu(L)(2)((HL)-L-2)(NCS)(2)(NCS)(2) (1), [Ni(H2L)(2)][CuCo(L)(2)(H2L)(NCS)](2)Br-2.2H(2)O (2), and [CuCoCd(H2L)(2)(L)(2)(NCS)Br-2]-CH3OH (3) have been prepared using zerovalent copper; cobalt thiocyanate; nickel thiocyanate (1), nickel bromide (2), or cadmium bromide (3); and methanol solutions of diethanolamine in air. The most prominent feature of the structures of 1 and 2 is the formation of the "pentanuclear" aggregate {[Ni(H2L)(2)][CoCu(L)(2)(H2L)(NCS)]2}(2+) made up of two neutral [CoCu(L)(2)(H2L)(NCS)] units and the previously unknown cation [Ni(H2L)(2)](2+) "glued together" by strong complementary hydrogen bonds. With Cd2+ instead of Ni2+, a different structure is obtained: the [CoCu(L)(2)(H2L)(NCS)] unit is now linked to the Cd center through coordination of the oxygens of L groups on the Co atom to form the discrete heterotrimetallic molecular species 3. Cryomagnetic measurements of the compounds show that, in all cases, the magnetic behavior is paramagnetic; the polycrystalline EPR spectra contain signals due to monomeric copper species only. At the same time, the EPR spectra of frozen DMF and methanol solutions of 1-3 reveal the presence of triplet-state species that can be generated only by a coupling of the CU2+ centers within a dimer. The species responsible for the appearance of transitions within the triplet state are thought to be Cu(II) dimeric centers formed by aggregation of two {CuCo(H2L)(L)(2)} fragments of 1-3 present in solution. The residual monomeric spectra in the g approximate to 2 region are indicative of the existence of an equilibrium in solution between the dimeric and monomeric Cu(II) centers in aggregated and free {CuCo(H2L)(L)(2)} fragments, respectively, with varying degrees of stability. The fragmentation process of 1-3 in solution was screened by electrospray ionization mass spectrometry.

AB - The three novel heterotrimetallic complexes [Ni(H2L)(2)][CoCu(L)(2)((HL)-L-2)(NCS)(2)(NCS)(2) (1), [Ni(H2L)(2)][CuCo(L)(2)(H2L)(NCS)](2)Br-2.2H(2)O (2), and [CuCoCd(H2L)(2)(L)(2)(NCS)Br-2]-CH3OH (3) have been prepared using zerovalent copper; cobalt thiocyanate; nickel thiocyanate (1), nickel bromide (2), or cadmium bromide (3); and methanol solutions of diethanolamine in air. The most prominent feature of the structures of 1 and 2 is the formation of the "pentanuclear" aggregate {[Ni(H2L)(2)][CoCu(L)(2)(H2L)(NCS)]2}(2+) made up of two neutral [CoCu(L)(2)(H2L)(NCS)] units and the previously unknown cation [Ni(H2L)(2)](2+) "glued together" by strong complementary hydrogen bonds. With Cd2+ instead of Ni2+, a different structure is obtained: the [CoCu(L)(2)(H2L)(NCS)] unit is now linked to the Cd center through coordination of the oxygens of L groups on the Co atom to form the discrete heterotrimetallic molecular species 3. Cryomagnetic measurements of the compounds show that, in all cases, the magnetic behavior is paramagnetic; the polycrystalline EPR spectra contain signals due to monomeric copper species only. At the same time, the EPR spectra of frozen DMF and methanol solutions of 1-3 reveal the presence of triplet-state species that can be generated only by a coupling of the CU2+ centers within a dimer. The species responsible for the appearance of transitions within the triplet state are thought to be Cu(II) dimeric centers formed by aggregation of two {CuCo(H2L)(L)(2)} fragments of 1-3 present in solution. The residual monomeric spectra in the g approximate to 2 region are indicative of the existence of an equilibrium in solution between the dimeric and monomeric Cu(II) centers in aggregated and free {CuCo(H2L)(L)(2)} fragments, respectively, with varying degrees of stability. The fragmentation process of 1-3 in solution was screened by electrospray ionization mass spectrometry.

U2 - 10.1021/ic048955w

DO - 10.1021/ic048955w

M3 - Article

VL - 43

SP - 7868

EP - 7876

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 9

ER -