A multi-O2 complex derived from a copper(I) dendrimer

Robertus J.M. Klein Gebbink; Anton W. Bosman; Martinus C. Feiters; E. W. Meijer; Roeland J.M. Nolte

doi:10.1002/(SICI)1521-3765(19990104)5:1<65::AID-CHEM65>3.0.CO;2-L

A multi-O₂ complex derived from a copper(I) dendrimer

Robertus J.M. Klein Gebbink, Anton W. Bosman, Martinus C. Feiters, E. W. Meijer, Roeland J.M. Nolte

Macromolecular and Organic Chemistry

Research output: Contribution to journal › Article › Academic › peer-review

41 Citations (Scopus)

Abstract

The high-pressure reaction of 2-vinylpyridine with the primary amines of four consecutive generations of poly(propylene imine) dendrimers (DAB-dendr- (NH₂)(n)) (n = 4, 8, 16, 32) yielded dendrimers with bis[2-(2- pyridyl)ethyl]-amine (PY2) ligands. The complexation of the new dendrimers with metal ions was investigated by a variety of techniques. The reaction of the first- and fourth-generation dendrimers (n=4 and 32, respectively) with Zn(II)(ClO₄)₂ was studied by ¹H NMR titration, and the complexation of all new dendrimers with Cu(II)(ClO₄)₂ was investigated by UV/Vis and EPR spectroscopy. Quantitative coordination of one metal ion per PY2 group was demonstrated in all cases. A UV/Vis titration of the fourth-generation dendrimer DAB-dendr-(PY2)₃₂ in dichloromethane with [Cu(I)(CH₃CN)₄](ClO₄) in acetonitrile revealed that approximately 30 Cu(I) ions were bound. Low-temperature UV/Vis spectroscopy of this complex in dichloromethane at -85°C in the presence of dioxygen showed that approximately 60-70% of the copper centers can bind dioxygen, corresponding to 10-11 of these molecules per dendrimer molecule. This complex can be considered a synthetic analogue of hemocyanin, the copper-containing oxygen transport protein from the hemolymph of molluscs and arthropods.

Original language	English
Pages (from-to)	65-69
Number of pages	5
Journal	Chemistry : A European Journal
Volume	5
Issue number	1
DOIs	https://doi.org/10.1002/(SICI)1521-3765(19990104)5:1<65::AID-CHEM65>3.0.CO;2-L
Publication status	Published - 1 Jan 1999

Keywords

Copper
Dendrimers
Dioxygen complexes
N ligands
Zinc

Access to Document

10.1002/(SICI)1521-3765(19990104)5:1<65::AID-CHEM65>3.0.CO;2-L

Cite this

@article{5e77827d5abb48d8b435a016467bb3f6,

title = "A multi-O2 complex derived from a copper(I) dendrimer",

abstract = "The high-pressure reaction of 2-vinylpyridine with the primary amines of four consecutive generations of poly(propylene imine) dendrimers (DAB-dendr- (NH2)(n)) (n = 4, 8, 16, 32) yielded dendrimers with bis[2-(2- pyridyl)ethyl]-amine (PY2) ligands. The complexation of the new dendrimers with metal ions was investigated by a variety of techniques. The reaction of the first- and fourth-generation dendrimers (n=4 and 32, respectively) with Zn(II)(ClO4)2 was studied by 1H NMR titration, and the complexation of all new dendrimers with Cu(II)(ClO4)2 was investigated by UV/Vis and EPR spectroscopy. Quantitative coordination of one metal ion per PY2 group was demonstrated in all cases. A UV/Vis titration of the fourth-generation dendrimer DAB-dendr-(PY2)32 in dichloromethane with [Cu(I)(CH3CN)4](ClO4) in acetonitrile revealed that approximately 30 Cu(I) ions were bound. Low-temperature UV/Vis spectroscopy of this complex in dichloromethane at -85°C in the presence of dioxygen showed that approximately 60-70% of the copper centers can bind dioxygen, corresponding to 10-11 of these molecules per dendrimer molecule. This complex can be considered a synthetic analogue of hemocyanin, the copper-containing oxygen transport protein from the hemolymph of molluscs and arthropods.",

keywords = "Copper, Dendrimers, Dioxygen complexes, N ligands, Zinc",

author = "{Klein Gebbink}, {Robertus J.M.} and Bosman, {Anton W.} and Feiters, {Martinus C.} and Meijer, {E. W.} and Nolte, {Roeland J.M.}",

year = "1999",

month = jan,

day = "1",

doi = "10.1002/(SICI)1521-3765(19990104)5:1<65::AID-CHEM65>3.0.CO;2-L",

language = "English",

volume = "5",

pages = "65--69",

journal = "Chemistry : A European Journal",

issn = "0947-6539",

publisher = "Wiley-VCH Verlag",

number = "1",

}

TY - JOUR

T1 - A multi-O2 complex derived from a copper(I) dendrimer

AU - Klein Gebbink, Robertus J.M.

AU - Bosman, Anton W.

AU - Feiters, Martinus C.

AU - Meijer, E. W.

AU - Nolte, Roeland J.M.

PY - 1999/1/1

Y1 - 1999/1/1

N2 - The high-pressure reaction of 2-vinylpyridine with the primary amines of four consecutive generations of poly(propylene imine) dendrimers (DAB-dendr- (NH2)(n)) (n = 4, 8, 16, 32) yielded dendrimers with bis[2-(2- pyridyl)ethyl]-amine (PY2) ligands. The complexation of the new dendrimers with metal ions was investigated by a variety of techniques. The reaction of the first- and fourth-generation dendrimers (n=4 and 32, respectively) with Zn(II)(ClO4)2 was studied by 1H NMR titration, and the complexation of all new dendrimers with Cu(II)(ClO4)2 was investigated by UV/Vis and EPR spectroscopy. Quantitative coordination of one metal ion per PY2 group was demonstrated in all cases. A UV/Vis titration of the fourth-generation dendrimer DAB-dendr-(PY2)32 in dichloromethane with [Cu(I)(CH3CN)4](ClO4) in acetonitrile revealed that approximately 30 Cu(I) ions were bound. Low-temperature UV/Vis spectroscopy of this complex in dichloromethane at -85°C in the presence of dioxygen showed that approximately 60-70% of the copper centers can bind dioxygen, corresponding to 10-11 of these molecules per dendrimer molecule. This complex can be considered a synthetic analogue of hemocyanin, the copper-containing oxygen transport protein from the hemolymph of molluscs and arthropods.

AB - The high-pressure reaction of 2-vinylpyridine with the primary amines of four consecutive generations of poly(propylene imine) dendrimers (DAB-dendr- (NH2)(n)) (n = 4, 8, 16, 32) yielded dendrimers with bis[2-(2- pyridyl)ethyl]-amine (PY2) ligands. The complexation of the new dendrimers with metal ions was investigated by a variety of techniques. The reaction of the first- and fourth-generation dendrimers (n=4 and 32, respectively) with Zn(II)(ClO4)2 was studied by 1H NMR titration, and the complexation of all new dendrimers with Cu(II)(ClO4)2 was investigated by UV/Vis and EPR spectroscopy. Quantitative coordination of one metal ion per PY2 group was demonstrated in all cases. A UV/Vis titration of the fourth-generation dendrimer DAB-dendr-(PY2)32 in dichloromethane with [Cu(I)(CH3CN)4](ClO4) in acetonitrile revealed that approximately 30 Cu(I) ions were bound. Low-temperature UV/Vis spectroscopy of this complex in dichloromethane at -85°C in the presence of dioxygen showed that approximately 60-70% of the copper centers can bind dioxygen, corresponding to 10-11 of these molecules per dendrimer molecule. This complex can be considered a synthetic analogue of hemocyanin, the copper-containing oxygen transport protein from the hemolymph of molluscs and arthropods.

KW - Copper

KW - Dendrimers

KW - Dioxygen complexes

KW - N ligands

KW - Zinc

UR - http://www.scopus.com/inward/record.url?scp=0032900152&partnerID=8YFLogxK

U2 - 10.1002/(SICI)1521-3765(19990104)5:1<65::AID-CHEM65>3.0.CO;2-L

DO - 10.1002/(SICI)1521-3765(19990104)5:1<65::AID-CHEM65>3.0.CO;2-L

M3 - Article

AN - SCOPUS:0032900152

SN - 0947-6539

VL - 5

SP - 65

EP - 69

JO - Chemistry : A European Journal

JF - Chemistry : A European Journal

IS - 1

ER -

A multi-O₂ complex derived from a copper(I) dendrimer

Abstract

Keywords

Access to Document

Other files and links

Fingerprint

Cite this