Thermal- and light-induced valence tautomerism with a concerted spin transition in an iron tris(diimine) complex.
Janetzki, Jett T.; Brown, Dominic S.; Daumann, Florian; Ismail, I. Haseena; Gable, Robert W.; Hay, Moya A.; Mulder, Roger J.; Starikova, Alyona A.; Weber, Birgit; Giansiracusa, Marcus J.; Boskovic, Colette; Chemical science 16 (2025) 5857–5871; doi:10.1039/d4sc07798a

data_1573979
_publ_section_title
;
 Thermal- and light-induced valence tautomerism with a concerted spin
 transition in an iron tris(diimine) complex.
;
_journal_issue                   14
_journal_name_full               'Chemical science'
_journal_page_first              5857
_journal_page_last               5871
_journal_paper_doi               10.1039/d4sc07798a
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C72 H48 Mn N6, 2(C24 H20 B), 1.5[C6H14O]'
_chemical_formula_sum            'C129 H109 B2 Mn N6 O1.5'
_chemical_formula_weight         1843.78
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2023-11-09
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-10-24 deposited with the CCDC.	2025-02-24 downloaded from the CCDC.
;
_cell_angle_alpha                80.9160(10)
_cell_angle_beta                 69.6040(10)
_cell_angle_gamma                60.143(2)
_cell_formula_units_Z            2
_cell_length_a                   17.0314(2)
_cell_length_b                   17.0463(3)
_cell_length_c                   21.0901(2)
_cell_measurement_reflns_used    46602
_cell_measurement_temperature    100.00(11)
_cell_measurement_theta_max      79.5940
_cell_measurement_theta_min      2.9860
_cell_volume                     4976.40(16)
_computing_cell_refinement       'CrysAlisPro 1.171.40.14a (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.40.14a (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.40.14a (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(11)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.980
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w   -122.00 -90.00   0.50    0.72    --  -47.26 -27.00 178.00   64
  2  \w     50.00 122.00   0.50    0.72    --   47.26  27.00 -18.00  144
  3  \w    -26.00  35.00   0.50    0.72    --   47.26 -27.00 178.00  122
  4  \w   -147.00-120.00   0.50    2.88    --  -91.75 -27.00 178.00   54
  5  \w    140.00 173.00   0.50    2.88    --  113.25  27.00 -18.00   66
  6  \w    102.00 134.00   0.50    2.88    --  113.25  27.00 -18.00   64
  7  \w    -80.00 -52.00   0.50    0.72    --  -47.26 125.00-150.00   56
  8  \w    -32.00  -5.00   0.50    0.72    --  -47.26  27.00 -18.00   54
  9  \w    -64.00 -37.00   0.50    0.72    --  -47.26 -27.00 178.00   54
 10  \w    -43.00  24.00   0.50    0.72    --  -47.26  57.00-120.00  134
 11  \w     40.00  85.00   0.50    0.72    --   47.26-125.00-120.00   90
 12  \w     23.00  77.00   0.50    0.72    --   47.26 -99.00-180.00  108
 13  \w    -23.00   4.00   0.50    0.72    --   47.26 -19.00   0.00   54
 14  \w     36.00  62.00   0.50    0.72    --   47.26 -57.00-120.00   52
 15  \w    -26.00  29.00   0.50    0.72    --   47.26 -19.00  60.00  110
 16  \w    -22.00  24.00   0.50    0.72    --   47.26 -57.00-120.00   92
 17  \w     43.00  90.00   0.50    0.72    --   47.26-125.00   0.00   94
 18  \w    -64.00 -22.00   0.50    2.88    --  -91.75 125.00  30.00   84
 19  \w    -50.00 -24.00   0.50    2.88    --  -91.75  45.00 150.00   52
 20  \w    136.00 164.00   0.50    2.88    --  113.25  15.00  60.00   56
 21  \w    100.00 130.00   0.50    2.88    --  113.25  15.00  60.00   60
 22  \w     44.00  70.00   0.50    2.88    --  113.25 -61.00 120.00   52
 23  \w     86.00 111.00   0.50    2.88    --  113.25-125.00 120.00   50
 24  \w     42.00  67.00   0.50    2.88    --  113.25 -61.00 -90.00   50
 25  \w     59.00 108.00   0.50    2.88    --  113.25-125.00-150.00   98
 26  \w     45.00  71.00   0.50    2.88    --  113.25 -61.00 -30.00   52
 27  \w     48.00 106.00   0.50    2.88    --  113.25 -94.00 120.00  116
 28  \w     52.00 107.00   0.50    2.88    --  113.25-105.00 -13.77  110
 29  \w     43.00  69.00   0.50    2.88    --  113.25 -93.00-110.56   52
 30  \w     44.00  69.00   0.50    2.88    --  113.25-125.00  90.00   50
 31  \w     79.00 111.00   0.50    2.88    --  113.25-125.00  90.00   64
 32  \w    120.00 176.00   0.50    2.88    --  113.25  15.00-150.00  112
 33  \w     42.00 105.00   0.50    2.88    --  113.25 -94.00  60.00  126
 34  \w    102.00 132.00   0.50    2.88    --  113.25  45.00 150.00   60
 35  \w    138.00 177.00   0.50    2.88    --  113.25  45.00 150.00   78
 36  \w    102.00 160.00   0.50    2.88    --  113.25  15.00 -60.00  116
 37  \w     43.00  69.00   0.50    2.88    --  113.25 -61.00-180.00   52
 38  \w     42.00  68.00   0.50    2.88    --  113.25 -61.00  30.00   52
 39  \w     74.00 107.00   0.50    2.88    --  113.25-104.00-144.73   66
 40  \w     43.00 101.00   0.50    2.88    --  113.25 -77.00 -90.00  116
 41  \w     43.00  68.00   0.50    2.88    --  113.25 -61.00  90.00   50
 42  \w     61.00 106.00   0.50    2.88    --  113.25 -94.00 150.00   90
 43  \w     42.00 102.00   0.50    2.88    --  113.25 -94.00-150.00  120
 44  \w    153.00 178.00   0.50    2.88    --  113.25 125.00 150.00   50
 45  \w     55.00 106.00   0.50    2.88    --  113.25 -94.00  30.00  102
 46  \w    109.00 135.00   0.50    2.88    --  113.25  61.00-150.00   52
 47  \w    144.00 177.00   0.50    2.88    --  113.25  61.00-150.00   66
 48  \w    105.00 173.00   0.50    2.88    --  113.25  30.00 120.00  136
 49  \w    106.00 135.00   0.50    2.88    --  113.25  77.00  60.00   58
 50  \w    151.00 177.00   0.50    2.88    --  113.25  77.00  60.00   52
 51  \w    109.00 135.00   0.50    2.88    --  113.25  61.00 120.00   52
 52  \w    152.00 177.00   0.50    2.88    --  113.25  61.00 120.00   50
 53  \w     42.00  67.00   0.50    2.88    --  113.25 -61.00   0.00   50
 54  \w     81.00 106.00   0.50    2.88    --  113.25 -93.00-110.56   50
 55  \w     96.00 168.00   0.50    2.88    --  113.25 125.00 -60.00  144
 56  \w    100.00 146.00   0.50    2.88    --  113.25 125.00 150.00   92
 57  \w     80.00 105.00   0.50    2.88    --  113.25 -94.00  90.00   50
 58  \w     42.00  71.00   0.50    2.88    --  113.25 -61.00  60.00   58
 59  \w     42.00  72.00   0.50    2.88    --  113.25 -77.00  60.00   60
 60  \w     76.00 101.00   0.50    2.88    --  113.25 -77.00  60.00   50
 61  \w     45.00 100.00   0.50    2.88    --  113.25 -77.00 -30.00  110
 62  \w    153.00 178.00   0.50    2.88    --  113.25  45.00-180.00   50
 63  \w    118.00 176.00   0.50    2.88    --  113.25  30.00 -60.00  116
 64  \w     47.00  72.00   0.50    2.88    --  113.25 -77.00-150.00   50
 65  \w     49.00 100.00   0.50    2.88    --  113.25 -94.00 -30.00  102
 66  \w     90.00 115.00   0.50    2.88    --  113.25 -84.00-102.64   50
 67  \w    111.00 136.00   0.50    2.88    --  113.25  30.00-180.00   50
 68  \w     62.00  87.00   0.50    2.88    --  113.25 -77.00 150.00   50
 69  \w     57.00 105.00   0.50    2.88    --  113.25 -94.00 -90.00   96
 70  \w     55.00  90.00   0.50    2.88    --  113.25-125.00 -60.00   70
 71  \w     45.00  70.00   0.50    2.88    --  113.25 -94.00   0.00   50
 72  \w    111.00 170.00   0.50    2.88    --  113.25  15.00 -90.00  118
 73  \w     53.00 108.00   0.50    2.88    --  113.25-108.00 -91.70  110
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0257217000
_diffrn_orient_matrix_UB_12      0.0997908000
_diffrn_orient_matrix_UB_13      0.0043593000
_diffrn_orient_matrix_UB_21      -0.1067933000
_diffrn_orient_matrix_UB_22      0.0268544000
_diffrn_orient_matrix_UB_23      0.0265230000
_diffrn_orient_matrix_UB_31      0.0033468000
_diffrn_orient_matrix_UB_32      -0.0135485000
_diffrn_orient_matrix_UB_33      0.0731659000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0504
_diffrn_reflns_av_unetI/netI     0.0379
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.980
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            96120
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.980
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.451
_diffrn_reflns_theta_min         2.990
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.521
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.160
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.14a (Rigaku Oxford Diffraction, 2018)
Numerical absorption correction based on gaussian integration over
			a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.230
_exptl_crystal_description       plate
_exptl_crystal_F_000             1944
_exptl_crystal_size_max          0.732
_exptl_crystal_size_mid          0.301
_exptl_crystal_size_min          0.022
_refine_diff_density_max         0.393
_refine_diff_density_min         -0.409
_refine_diff_density_rms         0.040
_refine_ls_extinction_coef       0.00024(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.101
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1389
_refine_ls_number_reflns         21372
_refine_ls_number_restraints     210
_refine_ls_restrained_S_all      1.106
_refine_ls_R_factor_all          0.0488
_refine_ls_R_factor_gt           0.0428
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0538P)^2^+1.2948P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1128
_refine_ls_wR_factor_ref         0.1181
_reflns_Friedel_coverage         0.000
_reflns_number_gt                18851
_reflns_number_total             21372
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07798a3.cif
_cod_data_source_block           jj4-029-dce-ipr2o-plates_redabs
_cod_depositor_comments
'Adding full bibliography for 1573969--1573979.cif.'
_cod_original_cell_volume        4976.40(15)
_cod_original_formula_sum        'C129 H109 B2 Mn N6 O1.50'
_cod_database_code               1573979
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C129 H98.5 B2 Mn N6 O1.5'
_chemical_oxdiff_usercomment     'red plates'
_olex2_refinement_description
;
1. Uiso/Uaniso restraints and constraints
C73 \\sim C73A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C74 \\sim C74A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C75 \\sim C75A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C76 \\sim C76A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C77 \\sim C77A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C78 \\sim C78A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C79 \\sim C79A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C80 \\sim C80A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C81 \\sim C81A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C82 \\sim C82A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C83 \\sim C83A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C84 \\sim C84A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C85 \\sim C85A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C86 \\sim C86A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C87 \\sim C87A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C88 \\sim C88A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C89 \\sim C89A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C90 \\sim C90A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C91 \\sim C91A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C92 \\sim C92A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C93 \\sim C93A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C94 \\sim C94A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C95 \\sim C95A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
C96 \\sim C96A: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
2. Same fragment restrains
{C73, C74, C75, C76, C77, C78, C79, C80, C81, C82, C83, C84, C85, C86, C87,
C88, C89, C90, C91, C92, C93, C94, C95, C96, B1} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C73A, C74A, C75A, C76A, C77A, C78A, C79A, C80A, C81A, C82A, C83A, C84A, C85A,
C86A, C87A, C88A, C89A, C90A, C91A, C92A, C93A, C94A, C95A, C96A, B1A}
3. Others
 Sof(C73A)=Sof(C74A)=Sof(H74A)=Sof(C75A)=Sof(H75A)=Sof(C76A)=Sof(H76A)=
 Sof(C77A)=Sof(H77A)=Sof(C78A)=Sof(H78A)=Sof(C79A)=Sof(C80A)=Sof(H80A)=
 Sof(C81A)=Sof(H81A)=Sof(C82A)=Sof(H82A)=Sof(C83A)=Sof(H83A)=Sof(C84A)=
 Sof(H84A)=Sof(C85A)=Sof(C86A)=Sof(H86A)=Sof(C87A)=Sof(H87A)=Sof(C88A)=
 Sof(H88A)=Sof(C89A)=Sof(H89A)=Sof(C90A)=Sof(H90A)=Sof(C91A)=Sof(C92A)=
 Sof(H92A)=Sof(C93A)=Sof(H93A)=Sof(C94A)=Sof(H94A)=Sof(C95A)=Sof(H95A)=
 Sof(C96A)=Sof(H96A)=Sof(B1A)=1-FVAR(1)
 Sof(C73)=Sof(C74)=Sof(H74)=Sof(C75)=Sof(H75)=Sof(C76)=Sof(H76)=Sof(C77)=
 Sof(H77)=Sof(C78)=Sof(H78)=Sof(C79)=Sof(C80)=Sof(H80)=Sof(C81)=Sof(H81)=
 Sof(C82)=Sof(H82)=Sof(C83)=Sof(H83)=Sof(C84)=Sof(H84)=Sof(C85)=Sof(C86)=
 Sof(H86)=Sof(C87)=Sof(H87)=Sof(C88)=Sof(H88)=Sof(C89)=Sof(H89)=Sof(C90)=
 Sof(H90)=Sof(C91)=Sof(C92)=Sof(H92)=Sof(C93)=Sof(H93)=Sof(C94)=Sof(H94)=
 Sof(C95)=Sof(H95)=Sof(C96)=Sof(H96)=Sof(B1)=FVAR(1)
4.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C14(H14), C15(H15),
 C16(H16), C17(H17), C18(H18), C20(H20), C21(H21), C22(H22), C23(H23), C24(H24),
  C28(H28), C29(H29), C30(H30), C32(H32), C33(H33), C34(H34), C38(H38),
 C39(H39), C40(H40), C41(H41), C42(H42), C44(H44), C45(H45), C46(H46), C47(H47),
  C48(H48), C52(H52), C53(H53), C54(H54), C56(H56), C57(H57), C58(H58),
 C62(H62), C63(H63), C64(H64), C65(H65), C66(H66), C68(H68), C69(H69), C70(H70),
  C71(H71), C72(H72), C98(H98), C99(H99), C100(H100), C101(H101), C102(H102),
 C104(H104), C105(H105), C106(H106), C107(H107), C108(H108), C110(H110),
 C111(H111), C112(H112), C113(H113), C114(H114), C116(H116), C117(H117),
 C118(H118), C119(H119), C120(H120), C74(H74), C75(H75), C76(H76), C77(H77),
 C78(H78), C80(H80), C81(H81), C82(H82), C83(H83), C84(H84), C86(H86), C87(H87),
  C88(H88), C89(H89), C90(H90), C92(H92), C93(H93), C94(H94), C95(H95),
 C96(H96), C74A(H74A), C75A(H75A), C76A(H76A), C77A(H77A), C78A(H78A),
 C80A(H80A), C81A(H81A), C82A(H82A), C83A(H83A), C84A(H84A), C86A(H86A),
 C87A(H87A), C88A(H88A), C89A(H89A), C90A(H90A), C92A(H92A), C93A(H93A),
 C94A(H94A), C95A(H95A), C96A(H96A)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              30762
_shelx_fab_checksum              68062
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.680
_oxdiff_exptl_absorpt_empirical_full_min 0.762