Site-Selective Photoswitching of Two Distinct Magnetic Chromophores in a Propeller-Like Molecule To Achieve Four Different Magnetic States.
Arczyński, Mirosław; Stanek, Jan; Sieklucka, Barbara; Dunbar, Kim R.; Pinkowicz, Dawid; Journal of the American Chemical Society  (2019) –; doi:10.1021/jacs.9b09576

data_4129185
_publ_section_title
;
 Site-Selective Photoswitching of Two Distinct Magnetic Chromophores in a
 Propeller-Like Molecule To Achieve Four Different Magnetic States.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_paper_doi               10.1021/jacs.9b09576
_journal_year                    2019
_chemical_formula_moiety         'C144 H128 Fe4 N32 W2'
_chemical_formula_sum            'C144 H128 Fe4 N32 W2'
_chemical_formula_weight         2897.87
_space_group_crystal_system      tetragonal
_space_group_IT_number           88
_space_group_name_Hall           '-I 4ad'
_space_group_name_H-M_alt        'I 41/a :2'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-07-23
_audit_creation_method
;
Olex2 1.2
(compiled 2017.02.23 svn.r3390 for OlexSys, GUI svn.r5320)
;
_audit_update_record
;
2017-08-03 # Formatted by publCIF

;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   23.5748(9)
_cell_length_b                   23.5748(9)
_cell_length_c                   62.588(3)
_cell_measurement_reflns_used    9937
_cell_measurement_temperature    173(2)
_cell_measurement_theta_max      26.51
_cell_measurement_theta_min      2.81
_cell_volume                     34785(3)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_temperature      173(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device_type  'Bruker D8 Quest Eco Photon 50'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0789
_diffrn_reflns_av_unetI/netI     0.0470
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       27
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       71
_diffrn_reflns_limit_l_min       -71
_diffrn_reflns_number            94342
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.107
_diffrn_reflns_theta_max         24.107
_diffrn_reflns_theta_min         2.303
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.691
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.5683
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0896 before and 0.0746 after correction.
The Ratio of minimum to maximum transmission is 0.7624.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.107
_exptl_crystal_description       block
_exptl_crystal_F_000             11744
_exptl_crystal_size_max          0.28
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.2
_platon_squeeze_details
;
TITL MAD055_Fe4W2_Temp_0m in I4(1)/a
CELL   23.5748   23.5748   62.5880     90.00     90.00     90.00
SPGR I41/a
Q101 0.085 0.859 0.113 !       3.99 eA-3
Q102 0.695 0.837 0.128 !       3.73 eA-3
C103 0.719 0.639 0.086 !       3.57 eA-3
Q104 0.211 0.140 0.123 !       3.49 eA-3
Q105 0.416 0.139 0.130 !       2.78 eA-3
C106 0.921 0.462 0.171 !       2.62 eA-3
Q107 0.877 0.259 0.126 !       2.61 eA-3
C108 0.566 0.762 0.120 !       2.56 eA-3
Q109 0.556 0.983 0.081 !       2.54 eA-3
C110 0.983 0.324 0.078 !       2.42 eA-3
C111 0.922 0.456 0.082 !       2.38 eA-3
C112 0.475 0.621 0.173 !       2.37 eA-3
Q113 0.421 0.132 0.168 !       2.32 eA-3
Q114 0.694 0.668 0.133 !       2.28 eA-3
C115 0.213 0.259 0.157 !       2.26 eA-3
Q116 0.438 0.164 0.163 !       2.26 eA-3
Q117 0.117 0.171 0.918 !       2.24 eA-3
Q118 0.128 0.650 0.172 !       2.20 eA-3
C119 0.140 0.232 0.157 !       2.17 eA-3
C120 0.484 0.633 0.077 !       2.09 eA-3
Q121 0.394 0.509 0.074 !       2.03 eA-3
C122 0.436 0.710 0.136 !       2.01 eA-3
C123 0.414 0.782 0.062 !       2.00 eA-3
Q124 0.625 0.538 0.175 !       1.98 eA-3
C125 0.623 0.712 0.168 !       1.92 eA-3
C126 0.914 0.476 0.078 !       1.89 eA-3
Q127 0.101 0.054 0.107 !       1.87 eA-3
Q128 0.281 0.447 0.122 !       1.86 eA-3
Q129 0.117 0.883 0.135 !       1.84 eA-3
C130 0.710 0.144 0.199 !       1.84 eA-3
Q131 0.412 0.616 0.047 !       1.83 eA-3
C132 0.227 0.471 0.018 !       1.82 eA-3
C133 0.491 0.631 0.121 !       1.81 eA-3
C134 0.390 0.725 0.078 !       1.79 eA-3
C135 0.587 0.747 0.189 !       1.79 eA-3
C136 0.960 0.265 0.192 !       1.79 eA-3
C137 0.980 0.141 0.085 !       1.76 eA-3
Q138 0.263 0.329 0.067 !       1.75 eA-3
C139 0.580 0.977 0.215 !       1.73 eA-3
Q140 0.578 0.484 0.685 !       1.73 eA-3
Q141 0.050 0.664 0.149 !       1.72 eA-3
C142 0.492 0.651 0.102 !       1.71 eA-3
C143 0.008 0.849 0.398 !       1.71 eA-3
C144 0.479 0.827 0.044 !       1.71 eA-3
C145 0.483 0.743 0.200 !       1.71 eA-3
Q146 0.194 0.155 0.080 !       1.71 eA-3
C147 0.228 0.979 0.207 !       1.70 eA-3
C148 0.057 0.235 0.089 !       1.69 eA-3
C149 0.771 0.491 0.008 !       1.69 eA-3
C150 0.016 0.345 0.611 !       1.68 eA-3
Q151 0.952 0.006 0.243 !       1.68 eA-3
Q152 0.580 0.196 0.118 !       1.67 eA-3
C153 0.667 0.992 0.205 !       1.66 eA-3
Q154 0.772 0.280 0.081 !       1.66 eA-3
C155 0.963 0.391 0.091 !       1.65 eA-3
Q156 0.366 0.873 0.144 !       1.65 eA-3
C157 0.217 0.404 0.054 !       1.64 eA-3
C158 0.009 0.196 0.182 !       1.64 eA-3
Q159 0.241 0.805 0.097 !       1.64 eA-3
Q160 0.186 0.474 0.063 !       1.63 eA-3
C161 0.040 0.234 0.059 !       1.63 eA-3
C162 0.553 0.976 0.181 !       1.62 eA-3
Q163 0.079 0.807 0.117 !       1.60 eA-3
C164 0.977 0.216 0.128 !       1.60 eA-3
C165 0.583 0.809 0.184 !       1.60 eA-3
C166 0.985 0.313 0.168 !       1.60 eA-3
Q167 0.680 0.921 0.219 !       1.59 eA-3
C168 0.361 0.012 0.246 !       1.59 eA-3
Q169 0.310 0.846 0.159 !       1.59 eA-3
Q170 0.697 0.464 0.117 !       1.58 eA-3
C171 0.470 0.436 0.230 !       1.58 eA-3
C172 0.061 0.181 0.072 !       1.58 eA-3
Q173 0.721 0.653 0.109 !       1.57 eA-3
Q174 0.493 0.559 0.107 !       1.57 eA-3
Q175 0.922 0.469 0.122 !       1.57 eA-3
C176 0.711 0.005 0.218 !       1.56 eA-3
Q177 0.998 0.809 0.086 !       1.56 eA-3
Q178 0.532 0.915 0.230 !       1.56 eA-3
C179 0.791 0.512 0.024 !       1.55 eA-3
C180 0.539 0.694 0.184 !       1.55 eA-3
Q181 0.313 0.074 0.022 !       1.55 eA-3
C182 0.390 0.517 0.238 !       1.54 eA-3
Q183 0.531 0.607 0.120 !       1.54 eA-3
C184 0.055 0.266 0.148 !       1.54 eA-3
Q185 0.470 0.169 0.172 !       1.54 eA-3
Q186 0.968 0.522 0.218 !       1.54 eA-3
Q187 0.139 0.071 0.167 !       1.54 eA-3
Q188 0.500 0.255 0.129 !       1.54 eA-3
C189 0.469 0.773 0.205 !       1.53 eA-3
Q190 0.262 0.748 0.023 !       1.53 eA-3
Q191 0.227 0.253 0.075 !       1.53 eA-3
Q192 0.477 0.970 0.176 !       1.53 eA-3
C193 0.799 0.677 0.008 !       1.53 eA-3
Q194 0.587 0.323 0.114 !       1.52 eA-3
Q195 0.881 0.671 0.085 !       1.52 eA-3
Q196 0.881 0.465 0.133 !       1.52 eA-3
Q197 0.696 0.668 0.195 !       1.52 eA-3
C198 0.687 0.655 0.072 !       1.52 eA-3
C199 0.209 0.042 0.005 !       1.52 eA-3
;
_refine_diff_density_max         3.712
_refine_diff_density_min         -4.259
_refine_diff_density_rms         0.337
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.141
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     741
_refine_ls_number_reflns         13808
_refine_ls_number_restraints     732
_refine_ls_restrained_S_all      1.121
_refine_ls_R_factor_all          0.1919
_refine_ls_R_factor_gt           0.1777
_refine_ls_shift/su_max          0.006
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1161P)^2^+3839.7305P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.4108
_refine_ls_wR_factor_ref         0.4227
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12419
_reflns_number_total             13808
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b09576_si_008.cif
_cod_data_source_block           mad055_fe4w2_temp_0m_sq
_cod_original_cell_volume        34784(3)
_cod_original_sg_symbol_H-M      'I 41/a'
_cod_database_code               4129185
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.729
_shelx_estimated_absorpt_t_min   0.649
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.233(4)
 0.767(4)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C62-C63
 1.39 with sigma of 0.02
 C30-C31
 1.39 with sigma of 0.02
 C15-C14
 1.39 with sigma of 0.02
 C30-C28
 1.39 with sigma of 0.02
 C27-C38
 1.45 with sigma of 0.02
 C59-C60
 1.39 with sigma of 0.02
 C58-C59
 1.39 with sigma of 0.02
 C59-C58
 1.39 with sigma of 0.02
 C59-C70
 1.39 with sigma of 0.02
 C66-C67
 1.39 with sigma of 0.02
 C64-C66
 1.39 with sigma of 0.02
 C67-C72
 1.45 with sigma of 0.02
 C72-C68
 2.44 with sigma of 0.02
 C72-C66
 2.44 with sigma of 0.02
 C63-C64
 1.39 with sigma of 0.01
 C71-C66
 1.45 with sigma of 0.0001
 C67-C71
 2.44 with sigma of 0.02
 C71-C64
 2.44 with sigma of 0.02
 C15-C16
 1.39 with sigma of 0.02
 C3-N3
 1.14 with sigma of 0.02
 C23-C18
 1.45 with sigma of 0.01
 C43-C54
 1.45 with sigma of 0.02
 C14-C12
 1.4 with sigma of 0.02
 C21-C11
 2.44 with sigma of 0.02
 C21-C9
 2.44 with sigma of 0.02
 C21-C10
 1.45 with sigma of 0.01
 C31-C32
 1.39 with sigma of 0.02
 C40-C35
 1.45 with sigma of 0.02
 C39-C34
 1.45 with sigma of 0.02
 C54-C43
 1.45 with sigma of 0.02
 C53-C42
 1.45 with sigma of 0.02
 C24-C19
 1.45 with sigma of 0.02
 C11-C22
 1.45 with sigma of 0.02
 C29-C33
 1.39 with sigma of 0.02
 C55-C50
 1.45 with sigma of 0.02
 C56-C51
 1.45 with sigma of 0.02
 C51-C56
 1.5 with sigma of 0.02
 C37-C25
 2.45 with sigma of 0.02
 C37-C27
 2.45 with sigma of 0.02
 C26-C37
 1.5 with sigma of 0.01
4. Restrained planarity
 C57, C58, C59, C60, C61, N15, C65, C64, C63, C62, C66, C71, C72, C68, N16,
 C67, C70, C69
 with sigma of 0.001
 C21, C22, C11, C10, C12, C14, N9, C9, C13, C17, C16, C15, C23, C18, C19, C24,
 C20, N10
 with sigma of 0.1
 C34, C35, C40, C36, N12, C32, C39, C31, C30, C38, C27, C28, C29, C26, C33,
 N11, C25, C37
 with sigma of 0.01
5. Uiso/Uaniso restraints and constraints
C5 \\sim N5: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C2 \\sim N2: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
N2 \\sim C2: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C1 \\sim N1: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
N6 \\sim C6: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C69 \\sim C58: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C7 \\sim N7: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C57 \\sim C58 \\sim C59 \\sim C60 \\sim C61 \\sim N15 \\sim C65 \\sim C64 \\sim
C63 \\sim C62 \\sim C66 \\sim C71 \\sim C72 \\sim C68 \\sim N16 \\sim C67 \\sim
C70 \\sim C69: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.002
N3 \\sim C3: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
C9 \\sim C10: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C10 \\sim C11: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C13 \\sim C17: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C21 \\sim C10 \\sim C11 \\sim C22 \\sim C12 \\sim C13 \\sim C17 \\sim C16 \\sim
C15 \\sim C14 \\sim C9 \\sim N9 \\sim C20 \\sim N10 \\sim C19 \\sim C18 \\sim
C23 \\sim C24: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C34 \\sim C32: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C52 \\sim C51: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C51 \\sim C56: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
C56 \\sim C51 \\sim C50 \\sim C55 \\sim C48 \\sim C47 \\sim C46 \\sim C44 \\sim
C45 \\sim C49 \\sim C52 \\sim N14 \\sim N13 \\sim C41 \\sim C42 \\sim C53 \\sim
C43 \\sim C54: within 2A with sigma of 0.02 and sigma for terminal atoms of
0.002
C26 \\sim C37: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.004
C36 \\sim C35 \\sim C34 \\sim C32 \\sim C33 \\sim N12 \\sim C29 \\sim C31 \\sim
C30 \\sim C28 \\sim C27 \\sim C26 \\sim C25 \\sim N11 \\sim C38 \\sim C37 \\sim
C39 \\sim C40: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C63) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N8) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N3) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.08
Uanis(C53) \\sim Ueq, Uanis(C54) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(N4) \\sim Ueq, Uanis(C4) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C6) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C8) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C7) \\sim Ueq, Uanis(N7) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C71) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C3) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(N13) \\sim Ueq: with sigma of 0.0001 and sigma for terminal atoms of
0.0002
Uanis(C44) \\sim Ueq: with sigma of 0.05 and sigma for terminal atoms of 0.1
Uanis(C24) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C34) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
6.a Aromatic/amide H refined with riding coordinates:
 C25(H25), C52(H52), C62(H62), C41(H41), C57(H57), C31(H31), C68(H68), C9(H9),
 C20(H20), C47(H47), C46(H46), C30(H30), C63(H63), C36(H36), C14(H14), C15(H15)
6.b Fitted hexagon refined as free rotating group:
 N11(C29,C28,C27,C26,C25), N14(C52,C51,C50,C48,C49), C41(N13,C45,C44,C43,C42),
 N15(C61,C60,C59,C58,C57), C67(C66,C64,C65,N16,C68), C13(C12,C11,C10,C9,N9),
 C17(N10,C20,C19,C18,C16), C35(C34,C32,C33,N12,C36)
6.c Idealised Me refined as rotating group:
 C70(H70A,H70B,H70C), C71(H71A,H71B,H71C), C69(H69A,H69B,H69C), C37(H37A,H37B,
 H37C), C23(H23A,H23B,H23C), C56(H56A,H56B,H56C), C53(H53A,H53B,H53C), C72(H72A,
 H72B,H72C), C38(H38A,H38B,H38C), C24(H24A,H24B,H24C), C54(H54A,H54B,H54C),
 C55(H55A,H55B,H55C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C40(H40A,H40B,
 H40C), C39(H39A,H39B,H39C)
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'