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

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.

Preparations, XPS and electronic spectroscopy, and magnetic properties of new one-dimensional cyano-bridged bimetallic assemblies, chiral [Cu(RR-chxn)2][Pd(CN)4] · 2H2O and [Cu(trans-chxn)2][M(CN)4] · 2H2O and [Cu(cis-chxn)2][M(CN)4] · 2H2O (M = Pd, Ni, Pt) (chxn = cyclohexane-(1,2)-diamine) have been investigated for tuning electronic properties by stereochemistry of the ligands and metal-substitution.Figure optionsDownload as PowerPoint slide