Extremely long axial Cu-N bonds in chiral one-dimensional zigzag cyanide-bridged CuII-NiII and CuII-Pt II bimetallic assemblies

Takashiro Akitsu, Yasuaki Einaga

研究成果: Article

34 引用 (Scopus)

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Preparations, crystal structures, and spectral and magnetic properties of two new chiral one-dimensional cyano-bridged coordination polymers, [Cu IIL2][MII(CN)4]·2H 2O (MII = NiII (1) and PtII (2), L = trans-cyclohexane-(1 R,2R)-diamine) have been presented. Complex 1 crystallizes in the monoclinic P21 space group with a = 9.864(4) Å, b = 15.393(8) Å, c = 7.995(4) Å, β = 110.32(3)°, V = 1138.4(10) Å3, and Z = 2, while 2 crystallizes in the monoclinic P2 1 space group with a = 9.899(3) Å, b = 15.541(4) Å, c = 8.102(2) Å, β = 111.02(2)°, V = 1163.6(5) Å3, and Z = 2. The unique zigzag cyano-bridged chains along the crystallographic b axis consist of alternate chiral [CuL2]2+ cations and square-planar [M(CN)4]2- anions. One side of the axial Cu-N(≡C) bond distances are 2.324(6) and 2.34(1) Å with Cu-N≡C angles of 137.8(6)° and 138.2(9)° for 1 and 2, respectively. On the other hand, the opposite side of the axial Cu-N(≡C) bond distances are 3.120(8) and 3.09(1) Å with significantly large bent Cu-N≡C angles of 97.9(5)° and 96.8(7)° for 1 and 2, respectively. The novel axial bonding features of extremely long semi-coordination Cu-N bonds are attributed to coexistence of pseudo-Jahn-Teller elongation and electrostatic interaction in the unique zigzag cyano-bridged chains. The characteristic bonding features with overlap between small 3d (NiII) or large 5d (PtII) and 3d (CuII) orbitals results in larger shifts in XPS peaks of not only Cu2p1/2 and Cu2p3/2 but also Ni2p1/2 and Ni2p3/2 for 1 than those of 2, which is also consistent with weak antiferromagnetic interactions with Weiss constants of -5.31 and -5.94 K for 1 and 2, respectively. The d-d, π-π*, and CT bands in the electronic, CD, and MCD spectra for 1 and 2 in the solid state at room temperature are discussed from the viewpoint of magneto-optical properties.

元の言語English
ページ(範囲)9826-9833
ページ数8
ジャーナルInorganic Chemistry
45
発行部数24
DOI
出版物ステータスPublished - 2006 11 27

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Cyanides
cyanides
assemblies
Diamines
diamines
Coulomb interactions
coordination polymers
electronic spectra
cyclohexane
elongation
Anions
Cations
Elongation
Magnetic properties
Polymers
X ray photoelectron spectroscopy
Optical properties
Crystal structure
electrostatics
magnetic properties

ASJC Scopus subject areas

  • Inorganic Chemistry

これを引用

@article{1823cf4b788b4ee28485f3f2a3f1a1b2,
title = "Extremely long axial Cu-N bonds in chiral one-dimensional zigzag cyanide-bridged CuII-NiII and CuII-Pt II bimetallic assemblies",
abstract = "Preparations, crystal structures, and spectral and magnetic properties of two new chiral one-dimensional cyano-bridged coordination polymers, [Cu IIL2][MII(CN)4]·2H 2O (MII = NiII (1) and PtII (2), L = trans-cyclohexane-(1 R,2R)-diamine) have been presented. Complex 1 crystallizes in the monoclinic P21 space group with a = 9.864(4) {\AA}, b = 15.393(8) {\AA}, c = 7.995(4) {\AA}, β = 110.32(3)°, V = 1138.4(10) {\AA}3, and Z = 2, while 2 crystallizes in the monoclinic P2 1 space group with a = 9.899(3) {\AA}, b = 15.541(4) {\AA}, c = 8.102(2) {\AA}, β = 111.02(2)°, V = 1163.6(5) {\AA}3, and Z = 2. The unique zigzag cyano-bridged chains along the crystallographic b axis consist of alternate chiral [CuL2]2+ cations and square-planar [M(CN)4]2- anions. One side of the axial Cu-N(≡C) bond distances are 2.324(6) and 2.34(1) {\AA} with Cu-N≡C angles of 137.8(6)° and 138.2(9)° for 1 and 2, respectively. On the other hand, the opposite side of the axial Cu-N(≡C) bond distances are 3.120(8) and 3.09(1) {\AA} with significantly large bent Cu-N≡C angles of 97.9(5)° and 96.8(7)° for 1 and 2, respectively. The novel axial bonding features of extremely long semi-coordination Cu-N bonds are attributed to coexistence of pseudo-Jahn-Teller elongation and electrostatic interaction in the unique zigzag cyano-bridged chains. The characteristic bonding features with overlap between small 3d (NiII) or large 5d (PtII) and 3d (CuII) orbitals results in larger shifts in XPS peaks of not only Cu2p1/2 and Cu2p3/2 but also Ni2p1/2 and Ni2p3/2 for 1 than those of 2, which is also consistent with weak antiferromagnetic interactions with Weiss constants of -5.31 and -5.94 K for 1 and 2, respectively. The d-d, π-π*, and CT bands in the electronic, CD, and MCD spectra for 1 and 2 in the solid state at room temperature are discussed from the viewpoint of magneto-optical properties.",
author = "Takashiro Akitsu and Yasuaki Einaga",
year = "2006",
month = "11",
day = "27",
doi = "10.1021/ic060783a",
language = "English",
volume = "45",
pages = "9826--9833",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "24",

}

TY - JOUR

T1 - Extremely long axial Cu-N bonds in chiral one-dimensional zigzag cyanide-bridged CuII-NiII and CuII-Pt II bimetallic assemblies

AU - Akitsu, Takashiro

AU - Einaga, Yasuaki

PY - 2006/11/27

Y1 - 2006/11/27

N2 - Preparations, crystal structures, and spectral and magnetic properties of two new chiral one-dimensional cyano-bridged coordination polymers, [Cu IIL2][MII(CN)4]·2H 2O (MII = NiII (1) and PtII (2), L = trans-cyclohexane-(1 R,2R)-diamine) have been presented. Complex 1 crystallizes in the monoclinic P21 space group with a = 9.864(4) Å, b = 15.393(8) Å, c = 7.995(4) Å, β = 110.32(3)°, V = 1138.4(10) Å3, and Z = 2, while 2 crystallizes in the monoclinic P2 1 space group with a = 9.899(3) Å, b = 15.541(4) Å, c = 8.102(2) Å, β = 111.02(2)°, V = 1163.6(5) Å3, and Z = 2. The unique zigzag cyano-bridged chains along the crystallographic b axis consist of alternate chiral [CuL2]2+ cations and square-planar [M(CN)4]2- anions. One side of the axial Cu-N(≡C) bond distances are 2.324(6) and 2.34(1) Å with Cu-N≡C angles of 137.8(6)° and 138.2(9)° for 1 and 2, respectively. On the other hand, the opposite side of the axial Cu-N(≡C) bond distances are 3.120(8) and 3.09(1) Å with significantly large bent Cu-N≡C angles of 97.9(5)° and 96.8(7)° for 1 and 2, respectively. The novel axial bonding features of extremely long semi-coordination Cu-N bonds are attributed to coexistence of pseudo-Jahn-Teller elongation and electrostatic interaction in the unique zigzag cyano-bridged chains. The characteristic bonding features with overlap between small 3d (NiII) or large 5d (PtII) and 3d (CuII) orbitals results in larger shifts in XPS peaks of not only Cu2p1/2 and Cu2p3/2 but also Ni2p1/2 and Ni2p3/2 for 1 than those of 2, which is also consistent with weak antiferromagnetic interactions with Weiss constants of -5.31 and -5.94 K for 1 and 2, respectively. The d-d, π-π*, and CT bands in the electronic, CD, and MCD spectra for 1 and 2 in the solid state at room temperature are discussed from the viewpoint of magneto-optical properties.

AB - Preparations, crystal structures, and spectral and magnetic properties of two new chiral one-dimensional cyano-bridged coordination polymers, [Cu IIL2][MII(CN)4]·2H 2O (MII = NiII (1) and PtII (2), L = trans-cyclohexane-(1 R,2R)-diamine) have been presented. Complex 1 crystallizes in the monoclinic P21 space group with a = 9.864(4) Å, b = 15.393(8) Å, c = 7.995(4) Å, β = 110.32(3)°, V = 1138.4(10) Å3, and Z = 2, while 2 crystallizes in the monoclinic P2 1 space group with a = 9.899(3) Å, b = 15.541(4) Å, c = 8.102(2) Å, β = 111.02(2)°, V = 1163.6(5) Å3, and Z = 2. The unique zigzag cyano-bridged chains along the crystallographic b axis consist of alternate chiral [CuL2]2+ cations and square-planar [M(CN)4]2- anions. One side of the axial Cu-N(≡C) bond distances are 2.324(6) and 2.34(1) Å with Cu-N≡C angles of 137.8(6)° and 138.2(9)° for 1 and 2, respectively. On the other hand, the opposite side of the axial Cu-N(≡C) bond distances are 3.120(8) and 3.09(1) Å with significantly large bent Cu-N≡C angles of 97.9(5)° and 96.8(7)° for 1 and 2, respectively. The novel axial bonding features of extremely long semi-coordination Cu-N bonds are attributed to coexistence of pseudo-Jahn-Teller elongation and electrostatic interaction in the unique zigzag cyano-bridged chains. The characteristic bonding features with overlap between small 3d (NiII) or large 5d (PtII) and 3d (CuII) orbitals results in larger shifts in XPS peaks of not only Cu2p1/2 and Cu2p3/2 but also Ni2p1/2 and Ni2p3/2 for 1 than those of 2, which is also consistent with weak antiferromagnetic interactions with Weiss constants of -5.31 and -5.94 K for 1 and 2, respectively. The d-d, π-π*, and CT bands in the electronic, CD, and MCD spectra for 1 and 2 in the solid state at room temperature are discussed from the viewpoint of magneto-optical properties.

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U2 - 10.1021/ic060783a

DO - 10.1021/ic060783a

M3 - Article

C2 - 17112280

AN - SCOPUS:33846040833

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SP - 9826

EP - 9833

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 24

ER -