Coordination algorithms control molecular architecture (see abstract)

Yanhua Lan; Dietmar K. Kennepohl; Boujemaa Moubaraki; Keith S. Murray; John D. Cashion; Geoffrey B. Jameson; Sally Brooker

doi:10.1002/chem.200304915

Coordination algorithms control molecular architecture (see abstract)

Yanhua Lan
, Dietmar K. Kennepohl
, Boujemaa Moubaraki
, Keith S. Murray
, John D. Cashion
, Geoffrey B. Jameson
, Sally Brooker

Centre for Science

University of Otago
Monash University
Massey University

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

57 Citations (Scopus)

Abstract

The synthesis and characterisation of a pyridazine-containing two-armed grid ligand L2 (prepared from one equivalent of 3,6-diformylpyridazine and two equivalents of p-anisidine) and the resulting transition metal (Zn, Cu, Ni, Co, Fe, Mn) complexes (1-9) are reported. Single-crystal X-ray structure determinations revealed that the copper(I) complex had self-assembled as a [2 × 2] grid, [Cu^I₄(L2)₄][PF ₆]₄· (CH₃CN)(H₂O)(CH ₃CH₂OCH₂CH₃)_0.25 (2·(CH₃CN)(H₂O)(CH₃CH ₂OCH₂CH₃)_0.25), whereas the [Zn ₂(L2)₂(CH₃CN)₂(H₂O) ₂][ClO₄]₄·CH₃CN (1·CH₃CN), [Ni^II₂(L2) ₂(CH₃CN)₄][BF₄]₄· (CH₃CH₂OCH₂CH₃)_0.25 (5a·(CH₃CH₂OCH₂CH₃) _0.25) and [CO^II₂(L2)₂(H ₂O)₂(CH₃CN)₂][ClO₄] ₄·(H₂O)(CH₃CN)_0.5 (6a·(H₂O)(CH₃CN)_0.5) complexes adopt a side-by-side architecture; iron(II) forms a monometallic cation binding three L2 ligands, [Fe^II(L2)₃][Fe^IIICl ₃OCl₃Fe^III]·CH₃CN (7·CH₃CN). A more soluble salt of the cation of 7, the diamagnetic complex [Fe^III(L2)₃][BF₄] ₂· 2H₂O (8), was prepared, as well as two derivatives of 2, [Cu^I₂(L2)₂(NCS) ₂]·H₂O (3) and [Cu^I ₂(L2)(NCS)₂] (4). The manganese complex, [Mn ^II₂(L2)₂Cl₄]·3H₂O (9), was not structurally characterised, but is proposed to adopt a side-by-side architecture. Variable temperature magnetic susceptibility studies yielded small negative J values for the side-by-side complexes: J = -21.6 cm^-1 and g = 2.17 for S = 1 dinickel(II) complex [Ni ^II₂(L2)₂(H₂O)4][BF₄] ₄ (5b) (fraction monomer 0.02); J = -7.6 cm^-1 and g = 2. 44 for S = 3/2 dicobalt(II) complex [Co^II₂(L2) ₂(H₂O)₄][ClO₄]₄ (6b) (fraction monomer 0.02); J = -3.2 cm^-1 and g = 1.95 for S = 5/2 dimanganese(II) complex 9 (fraction monomer 0.02). The double salt, mixed valent iron complex 7·H₂O gave J = -75 cm^-1 and g = 1.81 for the S = 1/2 diiron(III) anion (fraction monomer = 0.025). These parameters are lower than normal for Fe^IIIOFe^III m species because of fitting of superimposed monomer and dimer susceptibilities arising from trace impurities. The iron(II) centre in 7·H₂O is low spin and hence diamagnetic, a fact confirmed by the preparation and characterisation of the simple diamagnetic iron(II) complex 8. Mössbauer measurements at 77 K confirmed that there are two iron sites in 7·H ₂O, a low-spin iron(II) site and a high-spin diiron(III) site. A full electrochemical investigation was undertaken for complexes 1, 2, 5b, 6b and 8 and this showed that multiple redox processes are a feature of all of them.

Original language	English
Pages (from-to)	3772-3784
Number of pages	13
Journal	Chemistry - A European Journal
Volume	9
Issue number	16
DOIs	https://doi.org/10.1002/chem.200304915
Publication status	Published - 18 Aug 2003

Keywords

Bridging
Electrochemistry
Ligand design
Ligands
Magnetochemistry
Self-assembly

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10.1002/chem.200304915

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@article{b7fbeac439e24a6f9a20c83987b18f95,

title = "Coordination algorithms control molecular architecture (see abstract)",

abstract = "The synthesis and characterisation of a pyridazine-containing two-armed grid ligand L2 (prepared from one equivalent of 3,6-diformylpyridazine and two equivalents of p-anisidine) and the resulting transition metal (Zn, Cu, Ni, Co, Fe, Mn) complexes (1-9) are reported. Single-crystal X-ray structure determinations revealed that the copper(I) complex had self-assembled as a [2 × 2] grid, [CuI4(L2)4][PF 6]4· (CH3CN)(H2O)(CH 3CH2OCH2CH3)0.25 (2·(CH3CN)(H2O)(CH3CH 2OCH2CH3)0.25), whereas the [Zn 2(L2)2(CH3CN)2(H2O) 2][ClO4]4·CH3CN (1·CH3CN), [NiII2(L2) 2(CH3CN)4][BF4]4· (CH3CH2OCH2CH3)0.25 (5a·(CH3CH2OCH2CH3) 0.25) and [COII2(L2)2(H 2O)2(CH3CN)2][ClO4] 4·(H2O)(CH3CN)0.5 (6a·(H2O)(CH3CN)0.5) complexes adopt a side-by-side architecture; iron(II) forms a monometallic cation binding three L2 ligands, [FeII(L2)3][FeIIICl 3OCl3FeIII]·CH3CN (7·CH3CN). A more soluble salt of the cation of 7, the diamagnetic complex [FeIII(L2)3][BF4] 2· 2H2O (8), was prepared, as well as two derivatives of 2, [CuI2(L2)2(NCS) 2]·H2O (3) and [CuI 2(L2)(NCS)2] (4). The manganese complex, [Mn II2(L2)2Cl4]·3H2O (9), was not structurally characterised, but is proposed to adopt a side-by-side architecture. Variable temperature magnetic susceptibility studies yielded small negative J values for the side-by-side complexes: J = -21.6 cm-1 and g = 2.17 for S = 1 dinickel(II) complex [Ni II2(L2)2(H2O)4][BF4] 4 (5b) (fraction monomer 0.02); J = -7.6 cm-1 and g = 2. 44 for S = 3/2 dicobalt(II) complex [CoII2(L2) 2(H2O)4][ClO4]4 (6b) (fraction monomer 0.02); J = -3.2 cm-1 and g = 1.95 for S = 5/2 dimanganese(II) complex 9 (fraction monomer 0.02). The double salt, mixed valent iron complex 7·H2O gave J = -75 cm-1 and g = 1.81 for the S = 1/2 diiron(III) anion (fraction monomer = 0.025). These parameters are lower than normal for FeIIIOFeIII m species because of fitting of superimposed monomer and dimer susceptibilities arising from trace impurities. The iron(II) centre in 7·H2O is low spin and hence diamagnetic, a fact confirmed by the preparation and characterisation of the simple diamagnetic iron(II) complex 8. M{\"o}ssbauer measurements at 77 K confirmed that there are two iron sites in 7·H 2O, a low-spin iron(II) site and a high-spin diiron(III) site. A full electrochemical investigation was undertaken for complexes 1, 2, 5b, 6b and 8 and this showed that multiple redox processes are a feature of all of them.",

keywords = "Bridging, Electrochemistry, Ligand design, Ligands, Magnetochemistry, Self-assembly",

author = "Yanhua Lan and Kennepohl, \{Dietmar K.\} and Boujemaa Moubaraki and Murray, \{Keith S.\} and Cashion, \{John D.\} and Jameson, \{Geoffrey B.\} and Sally Brooker",

year = "2003",

month = aug,

day = "18",

doi = "10.1002/chem.200304915",

language = "English",

volume = "9",

pages = "3772--3784",

number = "16",

}

TY - JOUR

T1 - Coordination algorithms control molecular architecture (see abstract)

AU - Lan, Yanhua

AU - Kennepohl, Dietmar K.

AU - Moubaraki, Boujemaa

AU - Murray, Keith S.

AU - Cashion, John D.

AU - Jameson, Geoffrey B.

AU - Brooker, Sally

PY - 2003/8/18

Y1 - 2003/8/18

N2 - The synthesis and characterisation of a pyridazine-containing two-armed grid ligand L2 (prepared from one equivalent of 3,6-diformylpyridazine and two equivalents of p-anisidine) and the resulting transition metal (Zn, Cu, Ni, Co, Fe, Mn) complexes (1-9) are reported. Single-crystal X-ray structure determinations revealed that the copper(I) complex had self-assembled as a [2 × 2] grid, [CuI4(L2)4][PF 6]4· (CH3CN)(H2O)(CH 3CH2OCH2CH3)0.25 (2·(CH3CN)(H2O)(CH3CH 2OCH2CH3)0.25), whereas the [Zn 2(L2)2(CH3CN)2(H2O) 2][ClO4]4·CH3CN (1·CH3CN), [NiII2(L2) 2(CH3CN)4][BF4]4· (CH3CH2OCH2CH3)0.25 (5a·(CH3CH2OCH2CH3) 0.25) and [COII2(L2)2(H 2O)2(CH3CN)2][ClO4] 4·(H2O)(CH3CN)0.5 (6a·(H2O)(CH3CN)0.5) complexes adopt a side-by-side architecture; iron(II) forms a monometallic cation binding three L2 ligands, [FeII(L2)3][FeIIICl 3OCl3FeIII]·CH3CN (7·CH3CN). A more soluble salt of the cation of 7, the diamagnetic complex [FeIII(L2)3][BF4] 2· 2H2O (8), was prepared, as well as two derivatives of 2, [CuI2(L2)2(NCS) 2]·H2O (3) and [CuI 2(L2)(NCS)2] (4). The manganese complex, [Mn II2(L2)2Cl4]·3H2O (9), was not structurally characterised, but is proposed to adopt a side-by-side architecture. Variable temperature magnetic susceptibility studies yielded small negative J values for the side-by-side complexes: J = -21.6 cm-1 and g = 2.17 for S = 1 dinickel(II) complex [Ni II2(L2)2(H2O)4][BF4] 4 (5b) (fraction monomer 0.02); J = -7.6 cm-1 and g = 2. 44 for S = 3/2 dicobalt(II) complex [CoII2(L2) 2(H2O)4][ClO4]4 (6b) (fraction monomer 0.02); J = -3.2 cm-1 and g = 1.95 for S = 5/2 dimanganese(II) complex 9 (fraction monomer 0.02). The double salt, mixed valent iron complex 7·H2O gave J = -75 cm-1 and g = 1.81 for the S = 1/2 diiron(III) anion (fraction monomer = 0.025). These parameters are lower than normal for FeIIIOFeIII m species because of fitting of superimposed monomer and dimer susceptibilities arising from trace impurities. The iron(II) centre in 7·H2O is low spin and hence diamagnetic, a fact confirmed by the preparation and characterisation of the simple diamagnetic iron(II) complex 8. Mössbauer measurements at 77 K confirmed that there are two iron sites in 7·H 2O, a low-spin iron(II) site and a high-spin diiron(III) site. A full electrochemical investigation was undertaken for complexes 1, 2, 5b, 6b and 8 and this showed that multiple redox processes are a feature of all of them.

AB - The synthesis and characterisation of a pyridazine-containing two-armed grid ligand L2 (prepared from one equivalent of 3,6-diformylpyridazine and two equivalents of p-anisidine) and the resulting transition metal (Zn, Cu, Ni, Co, Fe, Mn) complexes (1-9) are reported. Single-crystal X-ray structure determinations revealed that the copper(I) complex had self-assembled as a [2 × 2] grid, [CuI4(L2)4][PF 6]4· (CH3CN)(H2O)(CH 3CH2OCH2CH3)0.25 (2·(CH3CN)(H2O)(CH3CH 2OCH2CH3)0.25), whereas the [Zn 2(L2)2(CH3CN)2(H2O) 2][ClO4]4·CH3CN (1·CH3CN), [NiII2(L2) 2(CH3CN)4][BF4]4· (CH3CH2OCH2CH3)0.25 (5a·(CH3CH2OCH2CH3) 0.25) and [COII2(L2)2(H 2O)2(CH3CN)2][ClO4] 4·(H2O)(CH3CN)0.5 (6a·(H2O)(CH3CN)0.5) complexes adopt a side-by-side architecture; iron(II) forms a monometallic cation binding three L2 ligands, [FeII(L2)3][FeIIICl 3OCl3FeIII]·CH3CN (7·CH3CN). A more soluble salt of the cation of 7, the diamagnetic complex [FeIII(L2)3][BF4] 2· 2H2O (8), was prepared, as well as two derivatives of 2, [CuI2(L2)2(NCS) 2]·H2O (3) and [CuI 2(L2)(NCS)2] (4). The manganese complex, [Mn II2(L2)2Cl4]·3H2O (9), was not structurally characterised, but is proposed to adopt a side-by-side architecture. Variable temperature magnetic susceptibility studies yielded small negative J values for the side-by-side complexes: J = -21.6 cm-1 and g = 2.17 for S = 1 dinickel(II) complex [Ni II2(L2)2(H2O)4][BF4] 4 (5b) (fraction monomer 0.02); J = -7.6 cm-1 and g = 2. 44 for S = 3/2 dicobalt(II) complex [CoII2(L2) 2(H2O)4][ClO4]4 (6b) (fraction monomer 0.02); J = -3.2 cm-1 and g = 1.95 for S = 5/2 dimanganese(II) complex 9 (fraction monomer 0.02). The double salt, mixed valent iron complex 7·H2O gave J = -75 cm-1 and g = 1.81 for the S = 1/2 diiron(III) anion (fraction monomer = 0.025). These parameters are lower than normal for FeIIIOFeIII m species because of fitting of superimposed monomer and dimer susceptibilities arising from trace impurities. The iron(II) centre in 7·H2O is low spin and hence diamagnetic, a fact confirmed by the preparation and characterisation of the simple diamagnetic iron(II) complex 8. Mössbauer measurements at 77 K confirmed that there are two iron sites in 7·H 2O, a low-spin iron(II) site and a high-spin diiron(III) site. A full electrochemical investigation was undertaken for complexes 1, 2, 5b, 6b and 8 and this showed that multiple redox processes are a feature of all of them.

KW - Bridging

KW - Electrochemistry

KW - Ligand design

KW - Ligands

KW - Magnetochemistry

KW - Self-assembly

UR - https://www.scopus.com/pages/publications/0041413235

U2 - 10.1002/chem.200304915

DO - 10.1002/chem.200304915

M3 - Journal Article

AN - SCOPUS:0041413235

SN - 0947-6539

VL - 9

SP - 3772

EP - 3784

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 16

ER -

Coordination algorithms control molecular architecture (see abstract)

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