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_4129182
_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 Mn4 Mo2 N32'
_chemical_formula_sum            'C144 H128 Mn4 Mo2 N32'
_chemical_formula_weight         2718.43
_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             2017-08-01
_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                   23.6836(10)
_cell_length_b                   23.6836(10)
_cell_length_c                   63.305(3)
_cell_measurement_reflns_used    9943
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      25.03
_cell_measurement_theta_min      2.79
_cell_volume                     35509(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      120.0
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0554
_diffrn_reflns_av_unetI/netI     0.0390
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       28
_diffrn_reflns_limit_h_min       -27
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       75
_diffrn_reflns_limit_l_min       -62
_diffrn_reflns_number            81828
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.082
_diffrn_reflns_theta_max         25.082
_diffrn_reflns_theta_min         2.281
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.461
_exptl_absorpt_correction_type   none
_exptl_crystal_density_diffrn    1.017
_exptl_crystal_description       block
_exptl_crystal_F_000             11200
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.33
_exptl_crystal_size_min          0.32
_platon_squeeze_details
;
TITL MAD107_Mn4W2_0m_I41a in I4(1)/a
CELL   23.6836   23.6836   63.3050     90.00     90.00     90.00
SPGR I41/a
C101 0.085 0.036 0.172 !       4.16 eA-3
C102 0.216 0.326 0.169 !       4.01 eA-3
C103 0.605 0.953 0.169 !       3.44 eA-3
Q104 0.804 0.359 0.125 !       3.44 eA-3
Q105 0.590 0.547 0.125 !       3.39 eA-3
Q106 0.898 0.626 0.127 !       2.91 eA-3
Q107 0.878 0.840 0.173 !       2.69 eA-3
C108 0.526 0.890 0.082 !       2.60 eA-3
C109 0.445 0.753 0.124 !       2.50 eA-3
Q110 0.408 0.319 0.125 !       2.49 eA-3
Q111 0.863 0.262 0.129 !       2.46 eA-3
Q112 0.304 0.859 0.167 !       2.42 eA-3
Q113 0.123 0.642 0.083 !       2.40 eA-3
C114 0.737 0.179 0.184 !       2.38 eA-3
Q115 0.431 0.155 0.167 !       2.33 eA-3
C116 0.514 0.942 0.086 !       2.01 eA-3
C117 0.986 0.558 0.414 !       2.01 eA-3
C118 0.548 0.992 0.191 !       1.98 eA-3
C119 0.077 0.985 0.195 !       1.93 eA-3
C120 0.946 0.242 0.172 !       1.88 eA-3
C121 0.969 0.549 0.419 !       1.88 eA-3
C122 0.509 0.492 0.234 !       1.86 eA-3
C123 0.992 0.306 0.168 !       1.86 eA-3
C124 0.244 0.026 0.214 !       1.81 eA-3
Q125 0.695 0.032 0.083 !       1.78 eA-3
Q126 0.339 0.804 0.147 !       1.78 eA-3
C127 0.472 0.616 0.173 !       1.78 eA-3
C128 0.221 0.466 0.016 !       1.77 eA-3
C129 0.773 0.132 0.026 !       1.75 eA-3
C130 0.415 0.484 0.204 !       1.72 eA-3
C131 0.102 0.022 0.190 !       1.69 eA-3
C132 0.919 0.538 0.058 !       1.65 eA-3
C133 0.726 0.466 0.226 !       1.65 eA-3
Q134 0.094 0.938 0.082 !       1.63 eA-3
Q135 0.780 0.166 0.197 !       1.62 eA-3
Q136 0.734 0.241 0.190 !       1.59 eA-3
C137 0.783 0.680 0.013 !       1.58 eA-3
Q138 0.743 0.703 0.174 !       1.57 eA-3
C139 0.533 0.931 0.147 !       1.55 eA-3
Q140 0.297 0.303 0.167 !       1.54 eA-3
Q141 0.854 0.801 0.204 !       1.53 eA-3
Q142 0.236 0.750 0.167 !       1.52 eA-3
C143 0.458 0.534 0.176 !       1.51 eA-3
C144 0.210 0.353 0.013 !       1.50 eA-3
C145 0.944 0.260 0.188 !       1.50 eA-3
C146 0.421 0.771 0.195 !       1.50 eA-3
C147 0.517 0.030 0.168 !       1.49 eA-3
C148 0.267 0.821 0.036 !       1.48 eA-3
C149 0.747 0.991 0.219 !       1.48 eA-3
C150 0.595 0.967 0.185 !       1.48 eA-3
Q151 0.884 0.035 0.214 !       1.47 eA-3
C152 0.189 0.261 0.168 !       1.45 eA-3
Q153 0.282 0.749 0.055 !       1.44 eA-3
C154 0.742 0.229 0.011 !       1.44 eA-3
C155 0.257 0.831 0.012 !       1.44 eA-3
C156 0.790 0.046 0.050 !       1.43 eA-3
C157 0.029 0.336 0.194 !       1.43 eA-3
Q158 0.711 0.522 0.054 !       1.43 eA-3
C159 0.437 0.006 0.239 !       1.42 eA-3
C160 0.999 0.127 0.078 !       1.42 eA-3
C161 0.523 0.019 0.237 !       1.41 eA-3
C162 0.954 0.305 0.182 !       1.41 eA-3
C163 0.418 0.705 0.184 !       1.41 eA-3
Q164 0.967 0.148 0.062 !       1.41 eA-3
Q165 0.466 0.578 0.034 !       1.41 eA-3
Q166 0.807 0.212 0.085 !       1.40 eA-3
Q167 0.009 0.576 0.086 !       1.40 eA-3
C168 0.662 0.673 0.060 !       1.40 eA-3
C169 0.432 0.671 0.096 !       1.39 eA-3
C170 0.391 0.696 0.096 !       1.39 eA-3
Q171 0.955 0.272 0.035 !       1.39 eA-3
C172 1.000 0.252 0.125 !       1.39 eA-3
Q173 0.306 0.468 0.168 !       1.38 eA-3
C174 0.726 0.228 0.175 !       1.38 eA-3
C175 0.697 0.992 0.234 !       1.38 eA-3
Q176 0.327 0.454 0.191 !       1.38 eA-3
Q177 0.569 0.435 0.128 !       1.37 eA-3
Q178 0.031 0.094 0.116 !       1.37 eA-3
Q179 0.917 0.945 0.204 !       1.36 eA-3
Q180 0.940 0.394 0.121 !       1.36 eA-3
C181 0.252 0.358 0.055 !       1.36 eA-3
C182 0.825 0.057 0.004 !       1.36 eA-3
C183 0.439 0.864 0.095 !       1.36 eA-3
C184 0.697 0.055 0.481 !       1.36 eA-3
C185 0.803 0.445 0.019 !       1.36 eA-3
C186 0.197 0.555 0.981 !       1.36 eA-3
Q187 0.133 0.172 0.149 !       1.35 eA-3
C188 0.174 0.952 0.215 !       1.35 eA-3
Q189 0.375 0.090 0.218 !       1.35 eA-3
C190 0.525 0.998 0.063 !       1.34 eA-3
Q191 0.148 0.711 0.238 !       1.34 eA-3
Q192 0.297 0.602 0.126 !       1.34 eA-3
C193 0.554 0.837 0.109 !       1.34 eA-3
C194 0.532 0.756 0.056 !       1.34 eA-3
C195 0.798 0.485 0.218 !       1.34 eA-3
C196 0.032 0.243 0.051 !       1.33 eA-3
C197 0.542 0.993 0.171 !       1.33 eA-3
C198 0.866 0.540 0.239 !       1.32 eA-3
Q199 0.062 0.125 0.060 !       1.32 eA-3
;
_refine_diff_density_max         1.532
_refine_diff_density_min         -1.170
_refine_diff_density_rms         0.159
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.796
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     789
_refine_ls_number_reflns         15724
_refine_ls_number_restraints     626
_refine_ls_restrained_S_all      1.829
_refine_ls_R_factor_all          0.1484
_refine_ls_R_factor_gt           0.1236
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3645
_refine_ls_wR_factor_ref         0.3976
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13049
_reflns_number_total             15724
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b09576_si_010.cif
_cod_data_source_block           mn4mo2_i41a_ok_sq
_cod_original_cell_volume        35508(3)
_cod_original_sg_symbol_H-M      'I 41/a'
_cod_database_code               4129182
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.867
_shelx_estimated_absorpt_t_min   0.855
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.582(3)
 0.418(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
 C34-C39
 1.45 with sigma of 0.01
 C40-C35
 1.45 with sigma of 0.01
 C11-C22
 1.45 with sigma of 0.02
 C4-N4
 1.14 with sigma of 0.01
 N3-C3
 1.14 with sigma of 0.01
 C64-C63
 1.39 with sigma of 0.02
 C63-C62
 1.39 with sigma of 0.02
 C62-C60
 1.39 with sigma of 0.02
 C61-C65
 1.39 with sigma of 0.02
 C71-C66
 1.45 with sigma of 0.02
 C23-C18
 1.45 with sigma of 0.02
 C15-C14
 1.39 with sigma of 0.02
 C14-C12
 1.39 with sigma of 0.02
 C17-C13
 1.39 with sigma of 0.02
 C16-C15
 1.39 with sigma of 0.02
 C32-C31
 1.39 with sigma of 0.02
 C31-C30
 1.39 with sigma of 0.02
 C30-C28
 1.39 with sigma of 0.02
 C29-C33
 1.39 with sigma of 0.02
 C27-C38
 1.45 with sigma of 0.005
 C26-C37
 1.45 with sigma of 0.005
4. Restrained planarity
 C71, C66, C67, C72, C68, C65, C64, N16
 with sigma of 0.1
 C37, C26, C27, C38, C28, C25, C29, C30, C31, C32, C34, C39, C40, C35, C36,
 C33, N12, N11
 with sigma of 0.1
5. Uiso/Uaniso restraints and constraints
C52 \\sim C51 \\sim C56 \\sim C50 \\sim C55 \\sim C48 \\sim C47 \\sim C46 \\sim
C44 \\sim C45 \\sim C49 \\sim C41 \\sim C42 \\sim C43 \\sim C54 \\sim C53:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C4 \\sim N4: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C3 \\sim N3: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C71 \\sim C66 \\sim C67 \\sim C72 \\sim C68 \\sim C65 \\sim C64 \\sim C63 \\sim
C62 \\sim C60 \\sim C61 \\sim C57 \\sim C58 \\sim C59 \\sim C69 \\sim C70:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C72 \\sim C67 \\sim C66 \\sim C71 \\sim C68 \\sim C65 \\sim C64 \\sim C63 \\sim
C62 \\sim C60 \\sim C61 \\sim C57 \\sim C58 \\sim C59 \\sim C69 \\sim C70:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C71 \\sim C66: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01
C24 \\sim C19 \\sim C18 \\sim C23: within 2A with sigma of 0.04 and sigma for
terminal atoms of 0.08
C20 \\sim C19 \\sim C24 \\sim C18 \\sim C23 \\sim C16 \\sim C17 \\sim C15 \\sim
C14 \\sim C12 \\sim C13 \\sim C9 \\sim C10 \\sim C11 \\sim C22 \\sim C21:
within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
C24 \\sim C19 \\sim C18 \\sim C23 \\sim C16 \\sim C14 \\sim C12 \\sim C11 \\sim
C22 \\sim C10 \\sim C21 \\sim C9 \\sim C13 \\sim C17 \\sim C20: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08
C37 \\sim C26 \\sim C38 \\sim C27: within 2A with sigma of 0.001 and sigma for
terminal atoms of 0.002
C37 \\sim C26 \\sim C27 \\sim C38 \\sim C28 \\sim C25: within 2A with sigma of
0.001 and sigma for terminal atoms of 0.002
C33 \\sim C29 \\sim N11 \\sim C25 \\sim C26 \\sim C27 \\sim C37 \\sim C38 \\sim
C28 \\sim C30 \\sim C31 \\sim C32 \\sim C34 \\sim C39 \\sim C35 \\sim C40 \\sim
C36: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C52) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C36) \\sim Ueq: with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C4) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C20) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C23)
\\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C17) \\sim Ueq,
Uanis(C15) \\sim Ueq, Uanis(C14) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C23) \\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C24)
\\sim Ueq: with sigma of 0.07 and sigma for terminal atoms of 0.14
Uanis(N10) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C37) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C38)
\\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C29) \\sim Ueq,
Uanis(C30) \\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C33)
\\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C35) \\sim Ueq,
Uanis(C36) \\sim Ueq, Uanis(C40) \\sim Ueq: with sigma of 0.08 and sigma for
terminal atoms of 0.16
6.a Aromatic/amide H refined with riding coordinates:
 C62(H62), C41(H41), C57(H57), C47(H47), C46(H46), C9(H9), C20(H20), C14(H14),
 C15(H15), C68(H68), C52(H52), C36(H36), C63(H63), C25(H25), C30(H30), C31(H31)
6.b Fitted hexagon refined as free rotating group:
 C18(C16,C17,N10,C20,C19), C65(N16,C68,C67,C66,C64), C36(N12,C33,C32,C34,C35),
 C25(N11,C29,C28,C27,C26)
6.c Idealised Me refined as rotating group:
 C24(H24A,H24B,H24C), C70(H70A,H70B,H70C), C71(H71A,H71B,H71C), C69(H69A,H69B,
 H69C), C23(H23A,H23B,H23C), C22(H22A,H22B,H22C), C56(H56A,H56B,H56C), C53(H53A,
 H53B,H53C), C72(H72A,H72B,H72C), C39(H39A,H39B,H39C), C38(H38A,H38B,H38C),
 C21(H21A,H21B,H21C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C37(H37A,H37B,
 H37C), C40(H40A,H40B,H40C)
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'