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_4129187
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2017-08-18
_audit_creation_method
;
Olex2 1.2
(compiled 2017.02.23 svn.r3390 for OlexSys, GUI svn.r5320)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   23.4200(9)
_cell_length_b                   23.4200(9)
_cell_length_c                   62.283(3)
_cell_measurement_reflns_used    9201
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      28.37
_cell_measurement_theta_min      2.83
_cell_volume                     34162(2)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(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  0.0741
_diffrn_reflns_av_unetI/netI     0.0462
_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       -27
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       73
_diffrn_reflns_limit_l_min       -73
_diffrn_reflns_number            97425
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.713
_diffrn_reflns_theta_max         24.713
_diffrn_reflns_theta_min         2.316
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.722
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.5704
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.0894 before and 0.0729 after correction. The Ratio of minimum to maximum transmission is 0.7649. The \l/2 correction factor is Not present.'
_exptl_crystal_density_diffrn    1.127
_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_fe4I 41/ak_slabsR = 0.16
CELL   23.4200   23.4200   62.2830     90.00     90.00     90.00
SPGR I41/a
Q101 0.076 0.858 0.125 !       4.03 eA-3
C102 0.290 0.848 0.086 !       3.99 eA-3
Q103 0.422 0.364 0.128 !       3.83 eA-3
Q104 0.408 0.159 0.114 !       2.89 eA-3
C105 0.104 0.025 0.078 !       2.84 eA-3
C106 0.224 0.343 0.070 !       2.64 eA-3
Q107 0.601 0.557 0.132 !       2.54 eA-3
Q108 0.906 0.657 0.089 !       2.49 eA-3
C109 0.491 0.836 0.129 !       2.45 eA-3
Q110 0.118 0.629 0.168 !       2.29 eA-3
Q111 0.227 0.152 0.133 !       2.27 eA-3
C112 0.581 0.965 0.188 !       2.23 eA-3
Q113 0.579 0.372 0.093 !       2.16 eA-3
C114 0.026 0.357 0.121 !       2.14 eA-3
Q115 0.584 0.372 0.116 !       2.11 eA-3
Q116 0.282 0.806 0.167 !       2.11 eA-3
Q117 0.436 0.497 0.176 !       2.08 eA-3
Q118 0.719 0.042 0.129 !       2.07 eA-3
Q119 0.717 0.460 0.129 !       2.07 eA-3
C120 0.240 0.304 0.079 !       2.04 eA-3
Q121 0.303 0.656 0.137 !       2.00 eA-3
C122 0.944 0.507 0.178 !       2.00 eA-3
C123 0.117 0.247 0.164 !       2.00 eA-3
Q124 0.112 0.036 0.137 !       1.90 eA-3
C125 0.758 0.196 0.174 !       1.90 eA-3
Q126 0.786 0.343 0.081 !       1.90 eA-3
Q127 0.291 0.857 0.176 !       1.89 eA-3
C128 0.751 0.688 0.181 !       1.89 eA-3
C129 0.578 0.712 0.086 !       1.89 eA-3
Q130 0.300 0.033 0.117 !       1.89 eA-3
C131 0.906 0.485 0.238 !       1.87 eA-3
Q132 0.422 0.179 0.172 !       1.87 eA-3
Q133 0.946 0.032 0.126 !       1.86 eA-3
Q134 0.600 0.148 0.067 !       1.86 eA-3
C135 0.893 0.261 0.652 !       1.85 eA-3
C136 0.393 0.761 0.152 !       1.85 eA-3
Q137 0.486 0.162 0.137 !       1.84 eA-3
C138 0.749 0.851 0.008 !       1.84 eA-3
C139 0.559 0.955 0.171 !       1.84 eA-3
C140 0.187 0.336 0.082 !       1.84 eA-3
C141 0.391 0.497 0.211 !       1.82 eA-3
C142 0.494 0.359 0.907 !       1.82 eA-3
C143 0.639 0.498 0.249 !       1.80 eA-3
Q144 0.266 0.385 0.175 !       1.80 eA-3
Q145 0.254 0.645 0.117 !       1.79 eA-3
Q146 0.095 0.676 0.114 !       1.78 eA-3
C147 0.914 0.193 0.083 !       1.77 eA-3
Q148 0.733 0.657 0.126 !       1.75 eA-3
C149 0.891 0.528 0.211 !       1.75 eA-3
C150 0.210 0.279 0.160 !       1.75 eA-3
Q151 0.705 0.672 0.156 !       1.74 eA-3
Q152 0.118 0.689 0.073 !       1.71 eA-3
C153 0.537 0.973 0.063 !       1.69 eA-3
C154 0.423 0.503 0.200 !       1.68 eA-3
C155 0.273 0.345 0.003 !       1.67 eA-3
Q156 0.398 0.528 0.094 !       1.64 eA-3
Q157 0.477 0.496 0.075 !       1.61 eA-3
C158 0.743 0.009 0.223 !       1.60 eA-3
Q159 0.391 0.189 0.131 !       1.60 eA-3
C160 0.415 0.471 0.215 !       1.59 eA-3
C161 0.554 0.034 0.195 !       1.59 eA-3
Q162 0.916 0.457 0.121 !       1.57 eA-3
C163 0.938 0.303 0.189 !       1.55 eA-3
C164 0.569 0.034 0.059 !       1.55 eA-3
C165 0.752 0.573 0.002 !       1.55 eA-3
C166 0.032 0.297 0.191 !       1.54 eA-3
Q167 0.211 0.367 0.093 !       1.53 eA-3
C168 0.991 0.222 0.055 !       1.53 eA-3
C169 0.789 0.514 0.231 !       1.53 eA-3
C170 0.718 0.519 0.235 !       1.52 eA-3
Q171 0.602 0.265 0.124 !       1.50 eA-3
Q172 0.407 0.348 0.051 !       1.50 eA-3
Q173 0.272 0.637 0.087 !       1.48 eA-3
C174 0.823 0.179 0.065 !       1.48 eA-3
Q175 0.703 0.658 0.141 !       1.48 eA-3
Q176 0.298 0.448 0.184 !       1.48 eA-3
Q177 0.703 0.155 0.860 !       1.47 eA-3
C178 0.320 0.466 0.040 !       1.47 eA-3
Q179 0.742 0.658 0.093 !       1.47 eA-3
C180 0.718 0.666 0.035 !       1.46 eA-3
C181 0.572 0.940 0.196 !       1.46 eA-3
Q182 0.070 0.025 0.215 !       1.44 eA-3
Q183 0.828 0.627 0.032 !       1.44 eA-3
C184 0.314 0.473 0.226 !       1.44 eA-3
C185 0.906 0.236 0.125 !       1.42 eA-3
Q186 0.908 0.027 0.135 !       1.42 eA-3
C187 0.241 0.019 0.231 !       1.41 eA-3
Q188 0.609 0.934 0.132 !       1.41 eA-3
Q189 0.041 0.014 0.191 !       1.40 eA-3
Q190 0.656 0.074 0.203 !       1.40 eA-3
Q191 0.470 0.014 0.181 !       1.40 eA-3
C192 0.250 0.315 0.050 !       1.40 eA-3
Q193 0.102 0.945 0.048 !       1.39 eA-3
C194 0.491 0.879 0.077 !       1.39 eA-3
C195 0.275 0.509 0.020 !       1.38 eA-3
Q196 0.473 0.163 0.171 !       1.38 eA-3
Q197 0.067 0.852 0.074 !       1.38 eA-3
C198 0.251 0.928 0.046 !       1.37 eA-3
Q199 0.288 0.442 0.086 !       1.37 eA-3
;
_refine_diff_density_max         4.182
_refine_diff_density_min         -3.784
_refine_diff_density_rms         0.316
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.057
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     801
_refine_ls_number_reflns         14556
_refine_ls_number_restraints     755
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.1693
_refine_ls_R_factor_gt           0.1496
_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^)+(0.1295P)^2^+2766.2722P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3561
_refine_ls_wR_factor_ref         0.3740
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12394
_reflns_number_total             14556
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b09576_si_007.cif
_cod_data_source_block           FE4W2_100K_SQ_ABcommented
_cod_depositor_comments
;

2021-04-11
Z value and formula fixed to values more according to usual
chemical conventions.                 miguel
;
_cod_original_formula_sum            'C288 H256 Fe8 N64 W4'
_cod_original_formula_weight         5795.75
_cod_original_formula_moiety         '2(C144 H128 Fe4 N32 W2)'
_cod_original_formula_units_Z            4
_cod_original_cell_volume        34162(3)
_cod_original_sg_symbol_H-M      'I 41/a'
_cod_database_code               4129187
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.725
_shelx_estimated_absorpt_t_min   0.644
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.222(3)
 0.778(3)
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
 C68-C69
 1.39 with sigma of 0.01
 C67-C68
 1.39 with sigma of 0.02
 C68-C67
 1.39 with sigma of 0.01
 C37-C26
 1.45 with sigma of 0.02
 C38-C27
 1.45 with sigma of 0.02
 C71-C59
 1.45 with sigma of 0.02
 C53-C42
 1.45 with sigma of 0.02
 C67-C72
 1.45 with sigma of 0.02
 C54-C43
 1.5 with sigma of 0.02
 C58-C70
 1.5 with sigma of 0.02
 N2-C2
 1.14 with sigma of 0.02
 C55-C50
 1.5 with sigma of 0.02
 C56-C51
 1.5 with sigma of 0.02
 C21-C10
 1.5 with sigma of 0.02
 C10-C21
 1.5 with sigma of 0.02
 C22-C11
 1.5 with sigma of 0.02
 C14-C15
 1.39 with sigma of 0.02
 C14-C12
 1.39 with sigma of 0.02
 C20-C19
 1.39 with sigma of 0.02
 C18-C23
 1.45 with sigma of 0.02
 C15-C16 = C15-C14
 1.39 with sigma of 0.1
 C15-C16
 1.39 with sigma of 0.02
 C17-C16
 1.39 with sigma of 0.02
 C16-C18
 1.39 with sigma of 0.02
 C18-C19
 1.39 with sigma of 0.02
 C19-C20
 1.39 with sigma of 0.02
 C41-N13
 1.37 with sigma of 0.02
 N13-C45
 1.37 with sigma of 0.02
 N10-C20
 1.37 with sigma of 0.02
 N10-C17
 1.37 with sigma of 0.02
 C3-N3
 1.14 with sigma of 0.02
 C37-C27
 2.6 with sigma of 0.04
4. Restrained planarity
 C36, C35, C34, C32, C29, N12, C39, C40
 with sigma of 0.05
 C60, C62, C63, C65, C66, C61
 with sigma of 0.1
 C66, C65, C67, C68, C69, N16, C72, C73
 with sigma of 0.1
5. Rigid bond restraints
 C5, N5
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C6, N6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C2, N2
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Uiso/Uaniso restraints and constraints
N8 \\sim C8: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C68 \\sim C69 \\sim C67: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02
C26 \\sim C37: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C33 \\sim C32 \\sim C34 \\sim C35 \\sim C36 \\sim N12 \\sim C40 \\sim C39:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C25 \\sim C26 \\sim C27 \\sim C28 \\sim C29 \\sim C30 \\sim C31 \\sim C32 \\sim
C33 \\sim N11 \\sim N12 \\sim C36 \\sim C35 \\sim C34 \\sim C40 \\sim C39 \\sim
C38 \\sim C37: within 2A with sigma of 0.03 and sigma for terminal atoms of 0.06
C38 \\sim C27: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
C59 \\sim C58: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C70 \\sim C58: within 2A with sigma of 0.002 and sigma for terminal atoms of
0.005
N2 \\sim C2: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
C63 \\sim C62: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C67 \\sim C68 \\sim C73 \\sim C72 \\sim C65 \\sim C69 \\sim C66 \\sim N16:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C71 \\sim C59 \\sim C58 \\sim C70 \\sim C57 \\sim N15 \\sim C61 \\sim C60 \\sim
C62 \\sim C63 \\sim C65 \\sim C66 \\sim N16 \\sim C69 \\sim C67 \\sim C68 \\sim
C72 \\sim C73: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C56 \\sim C51 \\sim C50 \\sim C55 \\sim C48 \\sim C47 \\sim C46 \\sim C44 \\sim
C43 \\sim C54 \\sim C42 \\sim C53 \\sim C41 \\sim C45 \\sim C49 \\sim N14 \\sim
C52: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C22 \\sim C11 \\sim C10 \\sim C12 \\sim C9 \\sim N9 \\sim C13 \\sim C17 \\sim
C21 \\sim C20: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C20 \\sim C17 \\sim C16 \\sim C18 \\sim C19 \\sim C23 \\sim C24 \\sim C15 \\sim
C14 \\sim C12 \\sim C13 \\sim N9 \\sim C9 \\sim C10 \\sim C11 \\sim C22 \\sim
C21: within 2A with sigma of 0.03 and sigma for terminal atoms of 0.06
N3 \\sim C3: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
C4 \\sim N4: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C27) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C37) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C54) \\sim Ueq: with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C53) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C7) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C24) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C21) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C68) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C39) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C72) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C40) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C72)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C34) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C32) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C35)
\\sim Ueq: with sigma of 0.03 and sigma for terminal atoms of 0.06
Uanis(C2) \\sim Ueq, Uanis(N2) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(C31) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C22)
\\sim Ueq, Uanis(C63) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C11) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C9) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C14) \\sim Ueq, Uanis(C15) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C19) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N13) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N10) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N3) \\sim Ueq, Uanis(C3) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(N11) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C8)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C4) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
7.a Aromatic/amide H refined with riding coordinates:
 C41(H41), C57(H57), C9(H9), C36(H36), C20(H20), C15(H15), C14(H14), C47(H47),
 C46(H46), C69(H69), C62(H62), C63(H63), C52(H52), C25(H25), C30(H30), C31(H31)
7.b Fitted hexagon refined as free rotating group:
 C9(C10,C11,C12,C13,N9), C65(C66,C61,C60,C62,C63), C32(C33,C29,C28,C30,C31)
7.c Idealised Me refined as rotating group:
 C71(H71A,H71B,H71C), C40(H40A,H40B,H40C), C70(H70A,H70B,H70C), C23(H23A,H23B,
 H23C), C56(H56A,H56B,H56C), C53(H53A,H53B,H53C), C38(H38A,H38B,H38C), C39(H39A,
 H39B,H39C), C24(H24A,H24B,H24C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C),
 C37(H37A,H37B,H37C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C73(H73A,H73B,
 H73C), C72(H72A,H72B,H72C)
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'