Abstract
Preparations, XPS and electronic spectroscopy, and magnetism of seven new one-dimensional cyano-bridged coordination polymers, chiral [Cu(RR-chxn)2][Pd(CN)4] · 2H2O (1), [Cu(trans-chxn)2][M(CN)4] · 2H2O (2, 4, and 6 for M = Pd, Ni, and Pt), and [Cu(cis-chxn)2][M(CN)4] · 2H2O (3, 5, and 7 for M = Pd, Ni, and Pt) (RR-chxn = cyclohexane-(1R,2R)-diamine, trans-chxn = racemic trans-cyclohexane-(1,2)-diamine, and cis-chxn = racemic cis-cyclohexane-(1,2)-diamine) have been reported in view of tuning of their electronic properties by stereochemistry of chxn ligands and metal-substitution. Comparison of Cu 2p1/2 and 2p3/2 peaks of XPS and broad d-d bands around 18 000 cm-1 of electronic spectra are described systematically for 1-7. Variable-temperature magnetic measurement shows that complexes 1-7 indicate weak antiferromagnetic interactions via cyano-bridges. Because of semi-coordination coupled with pseudo Jahn-Teller elongation and electrostatic interaction for 1, the axial Cu-N coordination bond distances of 2.330(7) and 3.092(8) Å are considerably longer than those of equatorial ones in the range from 2.016(6) to 2.030(6) Å. The former bond distances of 1 are intermediate values among the related Ni (2.324(6) and 3.120(8) Å) and Pt (2.34(1) and 3.09(1) Å) complexes.
| Original language | English |
|---|---|
| Pages (from-to) | 36-42 |
| Number of pages | 7 |
| Journal | Inorganica Chimica Acta |
| Volume | 361 |
| Issue number | 1 |
| DOIs | |
| Publication status | Published - 2008 Jan 1 |
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Keywords
- Copper(II)
- Nickel(II)
- Palladium(II)
- Platinum(II)
- XPS
ASJC Scopus subject areas
- Biochemistry
- Inorganic Chemistry
- Physical and Theoretical Chemistry
- Materials Chemistry
Cite this
Tuning of electronic properties of one-dimensional cyano-bridged CuII-NiII, CuII-PdII, and CuII-PtII bimetallic assemblies by stereochemistry of ligands. / Akitsu, Takashiro; Einaga, Yasuaki.
In: Inorganica Chimica Acta, Vol. 361, No. 1, 01.01.2008, p. 36-42.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Tuning of electronic properties of one-dimensional cyano-bridged CuII-NiII, CuII-PdII, and CuII-PtII bimetallic assemblies by stereochemistry of ligands
AU - Akitsu, Takashiro
AU - Einaga, Yasuaki
PY - 2008/1/1
Y1 - 2008/1/1
N2 - Preparations, XPS and electronic spectroscopy, and magnetism of seven new one-dimensional cyano-bridged coordination polymers, chiral [Cu(RR-chxn)2][Pd(CN)4] · 2H2O (1), [Cu(trans-chxn)2][M(CN)4] · 2H2O (2, 4, and 6 for M = Pd, Ni, and Pt), and [Cu(cis-chxn)2][M(CN)4] · 2H2O (3, 5, and 7 for M = Pd, Ni, and Pt) (RR-chxn = cyclohexane-(1R,2R)-diamine, trans-chxn = racemic trans-cyclohexane-(1,2)-diamine, and cis-chxn = racemic cis-cyclohexane-(1,2)-diamine) have been reported in view of tuning of their electronic properties by stereochemistry of chxn ligands and metal-substitution. Comparison of Cu 2p1/2 and 2p3/2 peaks of XPS and broad d-d bands around 18 000 cm-1 of electronic spectra are described systematically for 1-7. Variable-temperature magnetic measurement shows that complexes 1-7 indicate weak antiferromagnetic interactions via cyano-bridges. Because of semi-coordination coupled with pseudo Jahn-Teller elongation and electrostatic interaction for 1, the axial Cu-N coordination bond distances of 2.330(7) and 3.092(8) Å are considerably longer than those of equatorial ones in the range from 2.016(6) to 2.030(6) Å. The former bond distances of 1 are intermediate values among the related Ni (2.324(6) and 3.120(8) Å) and Pt (2.34(1) and 3.09(1) Å) complexes.
AB - Preparations, XPS and electronic spectroscopy, and magnetism of seven new one-dimensional cyano-bridged coordination polymers, chiral [Cu(RR-chxn)2][Pd(CN)4] · 2H2O (1), [Cu(trans-chxn)2][M(CN)4] · 2H2O (2, 4, and 6 for M = Pd, Ni, and Pt), and [Cu(cis-chxn)2][M(CN)4] · 2H2O (3, 5, and 7 for M = Pd, Ni, and Pt) (RR-chxn = cyclohexane-(1R,2R)-diamine, trans-chxn = racemic trans-cyclohexane-(1,2)-diamine, and cis-chxn = racemic cis-cyclohexane-(1,2)-diamine) have been reported in view of tuning of their electronic properties by stereochemistry of chxn ligands and metal-substitution. Comparison of Cu 2p1/2 and 2p3/2 peaks of XPS and broad d-d bands around 18 000 cm-1 of electronic spectra are described systematically for 1-7. Variable-temperature magnetic measurement shows that complexes 1-7 indicate weak antiferromagnetic interactions via cyano-bridges. Because of semi-coordination coupled with pseudo Jahn-Teller elongation and electrostatic interaction for 1, the axial Cu-N coordination bond distances of 2.330(7) and 3.092(8) Å are considerably longer than those of equatorial ones in the range from 2.016(6) to 2.030(6) Å. The former bond distances of 1 are intermediate values among the related Ni (2.324(6) and 3.120(8) Å) and Pt (2.34(1) and 3.09(1) Å) complexes.
KW - Copper(II)
KW - Nickel(II)
KW - Palladium(II)
KW - Platinum(II)
KW - XPS
UR - http://www.scopus.com/inward/record.url?scp=36549012176&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=36549012176&partnerID=8YFLogxK
U2 - 10.1016/j.ica.2007.06.034
DO - 10.1016/j.ica.2007.06.034
M3 - Article
AN - SCOPUS:36549012176
VL - 361
SP - 36
EP - 42
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
SN - 0020-1693
IS - 1
ER -