Tuning of electronic properties of one-dimensional cyano-bridged CuII-NiII, CuII-PdII, and CuII-PtII bimetallic assemblies by stereochemistry of ligands

Takashiro Akitsu, Yasuaki Einaga

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16 Citations (Scopus)

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 languageEnglish
Pages (from-to)36-42
Number of pages7
JournalInorganica Chimica Acta
Volume361
Issue number1
DOIs
Publication statusPublished - 2008 Jan 1

Fingerprint

Stereochemistry
stereochemistry
Cyclohexane
diamines
Electronic properties
cyclohexane
assemblies
X ray photoelectron spectroscopy
Tuning
Ligands
tuning
ligands
Diamines
Magnetic variables measurement
Magnetism
Coulomb interactions
Static Electricity
electronics
Temperature measurement
Elongation

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

@article{04bbbf77fa294880a754d011d85c2c7c,
title = "Tuning of electronic properties of one-dimensional cyano-bridged CuII-NiII, CuII-PdII, and CuII-PtII bimetallic assemblies by stereochemistry of ligands",
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) {\AA} are considerably longer than those of equatorial ones in the range from 2.016(6) to 2.030(6) {\AA}. The former bond distances of 1 are intermediate values among the related Ni (2.324(6) and 3.120(8) {\AA}) and Pt (2.34(1) and 3.09(1) {\AA}) complexes.",
keywords = "Copper(II), Nickel(II), Palladium(II), Platinum(II), XPS",
author = "Takashiro Akitsu and Yasuaki Einaga",
year = "2008",
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doi = "10.1016/j.ica.2007.06.034",
language = "English",
volume = "361",
pages = "36--42",
journal = "Inorganica Chimica Acta",
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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

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