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    ANO8A Magnetism 2018 PDF

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    Jelte de Wit
    This document discusses the magnetic properties of transition metal complexes. It introduces high-spin and low-spin states for d6 complexes, and how ligand field strength can induce spin transitions. Strong-field ligands stabilize low-spin states while weak-field ligands favor high-spin. The document also covers magnetic interactions between unpaired electrons, including paramagnetism, ferromagnetism, antiferromagnetism, and ferrimagnetism. Key characterization techniques for studying complex electronic structures are also summarized, such as NMR, EPR, IR and UV-Vis spectroscopy.

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    ANO8A Magnetism 2018 PDF

    Uploaded by

    Jelte de Wit
    68 views22 pages
    This document discusses the magnetic properties of transition metal complexes. It introduces high-spin and low-spin states for d6 complexes, and how ligand field strength can induce spin transitions. Strong-field ligands stabilize low-spin states while weak-field ligands favor high-spin. The document also covers magnetic interactions between unpaired electrons, including paramagnetism, ferromagnetism, antiferromagnetism, and ferrimagnetism. Key characterization techniques for studying complex electronic structures are also summarized, such as NMR, EPR, IR and UV-Vis spectroscopy.

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    This document discusses the magnetic properties of transition metal complexes. It introduces high-spin and low-spin states for d6 complexes, and how ligand field strength can induce spin transitions. Strong-field ligands stabilize low-spin states while weak-field ligands favor high-spin. The document also covers magnetic interactions between unpaired electrons, including paramagnetism, ferromagnetism, antiferromagnetism, and ferrimagnetism. Key characterization techniques for studying complex electronic structures are also summarized, such as NMR, EPR, IR and UV-Vis spectroscopy.

    Copyright:

    © All Rights Reserved
    Download as PDF, TXT or read online from Scribd
    Download as pdf or txt
    68 views22 pages

    ANO8A Magnetism 2018 PDF

    Uploaded by

    Jelte de Wit
    This document discusses the magnetic properties of transition metal complexes. It introduces high-spin and low-spin states for d6 complexes, and how ligand field strength can induce spin transitions. Strong-field ligands stabilize low-spin states while weak-field ligands favor high-spin. The document also covers magnetic interactions between unpaired electrons, including paramagnetism, ferromagnetism, antiferromagnetism, and ferrimagnetism. Key characterization techniques for studying complex electronic structures are also summarized, such as NMR, EPR, IR and UV-Vis spectroscopy.

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    You are on page 1of 22

    Magnetic properties

    of complexes

    MST - ANO 1
    HS and LS for d6 in Oh ***

    HS: LS:
    Fe2+ in [Fe(H2O)6]2+ Fe2+ in K4[Fe(CN)6]
    S = 2; paramagnetic S = 0; diamagnetic
    MST - ANO 2
    LFSE for weak and strong ligands *
    dn Oh weak S Oh strong S Extra  Td weak
    d0 0 0 0 0 0 0
    d1 4 Dq(O) ½ 4 Dq(O) ½ 0 6 Dq(T)
    d2 8 Dq(O) 1 8 Dq(O) 1 0 12 Dq(T)
    d3 12 Dq(O) 1½ 12 Dq(O) 1½ 0 8 Dq(T)
    d4 6 Dq(O) 2 16 Dq(O) 1 LS 1 4 Dq(T)
    d5 0 2½ 20 Dq(O) ½ LS 2 0
    d6 4 Dq(O) 2 24 Dq(O) 0 LS 2 6 Dq(T)
    d7 8 Dq(O) 1½ 18 Dq(O) ½ LS 1 12 Dq(T)
    d8 12 Dq(O) 1 12 Dq(O) 1 0 8 Dq(T)
    d9 6 Dq(O) ½ 6 Dq(O) ½ 0 4 Dq(T)
    d10 0 0 0 0 0 0
    MST - ANO 3
    Spin Transitions in Oh Fe(II) species

    Left: low spin


    Right: high spin
    Differences in:
    magnetism, optical
    properties, ligand
    exchange, redox,
    electron exchange
    MST - ANO 4
    Structure & magnetism of [Fe(bapbpy)(SCN)2]
    magnetism
    H
    IP S
    LS

    XRD

    Bonnet et al, Chem. Commun. 2008, 5619


    MST - ANO 5
    A peculiar symmetry breaking
    1.0

    0.8

    0.6
    HS

    0.4

    0.2

    0.0
    0 40 80 120 160 200 240 280

    T [K]

    X-ray crystal structure:


    - [LS-HS-LS] motif
    - long-range ordering
    - unprecedented 1:2 HS:LS ratio
    - symmetry breaking
    MST - ANO Bonnet et al, Chem. Commun. 2008, 5619 6
    The Gouy balance *

    MST - ANO 7
    Magnetic properties of complexes ***
    • Unpaired electrons in (high spin) complexes 
    magnetic moment 
    • : spin angular momentum
    + orbit angular momentum (can be ignored for 1st
    row transition metals)

    •  (spin only) = 2 S ( S  1) = n ( n  2)

    S = total electron spin; n = # unpaired electrons


    MST - ANO 8
    Spin-only values *
    Metal ion dn S eff (spin-only) Observed values
    /B eff /B
    Ti3+ d1 ½ 1.73 1.7 – 1.8
    V3+ d2 1 2.83 2.8 – 3.1
    V2+, Cr3+ d3 1½ 3.87 3.7 – 3.9
    Cr2+, Mn3+ d4 2 4.90 4.8 – 4.9
    Mn2+, Fe3+ d5 2½ 5.92 5.7 – 6.0
    Fe2+, Co3+ d6 2 4.90 5.0 – 5.6
    Co2+ d7 1½ 3.87 4.3 – 5.2

    MST - ANO 9
    Paramagnetic Pd2+ *

     = 2.48 B

    MST - ANO 10
    Magnetic ordering *
    ▪ the system contains magnetic moments
    ▪ there are magnetic interactions between the moments

    x x

    T>>Tc T ~ Tc T< Tc
    Critical temperature (Tc) – the temperature above which the material
    loses its magnetic ordering
    Spontaneous magnetization – describes the appearance
    MST - ANO
    of an ordered spin state at zero applied magnetic field 11
    Magnetic interactions ***

    paramagnetic ferromagnetic

    anti-ferromagnetic ferrimagnetic

    MST - ANO 12
    [Cu(L)]22+
    N SH
    N
    N

    Anti-ferromagnetic
    EPR silent
    NMR possible

    MST - ANO 13
    Characterization of metal compounds ***
    • IR spectroscopy
    • Mass spectrometry
    • UV-Vis spectroscopy (NOT for d10 or HS d5; why not?)

    • Diamagnetic: (S = 0; d10; LS d6 or d8; AF coupled


    systems)
    – NMR spectroscopy
    • Paramagnetic (e.g. d9, Cu(II))
    – EPR spectroscopy

    MST - ANO 14
    Nuclear Magnetic Resonance (NMR)

    Diamagnetic LS Co(III)

    MST - ANO 15
    NMR Paramagnetic HS Co(II)

    MST - ANO 16
    Electron Paramagnetic Resonance (EPR)

    Electron-spin flip
    in magnetic field

    [Cu(L)(H2O)]2+
    MST - ANO 17
    Trinuclear copper(II)
    Spin frustration

    [Cu3(OH)(6-mepao)3(PhCO2)2] [Cu3(OH)(6-mepao)3]2+

    MST - ANO A. Escuer, Eur.J.Inorg.Chem., 2014, 83 18


    [Mn4Gd2O2(RCOO)6(L)(NO3)2]

    2x MnIII –- S = 0 (AF)
    2x MnII –– S = 5
    2x GdIII –– S = 7
    (Green: JT axis) Total: S = 12
    MST - ANO G. Christou, Inorg.Chem., 2011, 50, 10476 19
    Intermediate spin

    MST - ANO 20
    Summary - keywords

    • Electron spin, HS, LS, intermediate spin


    • Magnetic moment, spin-only value
    • Spin-crossover HS – LS
    • Diamagnetic, paramagnetic
    • Magnetic ordering: anti-ferromagnetic, ferromagnetic,
    ferrimagnetic
    • Characterization techniques: IR, UV-Vis, NMR, EPR

    MST - ANO 21
    Assignment

    • Bestuderen: §21.1-21.3, 21.4a,b,c (p550-559);


    • Lezen: §27.1 – 27.3 (p820-826)

    MST - ANO 22

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