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_4129188
_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 N32 W2'
_chemical_formula_sum            'C144 H128 Mn4 N32 W2'
_chemical_formula_weight         2894.24
_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             2017-07-31
_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                   23.6740(14)
_cell_length_b                   23.6740(14)
_cell_length_c                   63.057(4)
_cell_measurement_reflns_used    9651
_cell_measurement_temperature    120(2)
_cell_measurement_theta_max      26.35
_cell_measurement_theta_min      2.80
_cell_volume                     35341(4)
_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(2)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.997
_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  0.1538
_diffrn_reflns_av_unetI/netI     0.0686
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       78
_diffrn_reflns_limit_l_min       -66
_diffrn_reflns_number            112927
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.467
_diffrn_reflns_theta_min         2.288
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.622
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.3988
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1283 before and 0.0890 after correction. The Ratio of minimum to maximum transmission is 0.5350. The \l/2 correction factor is Not present.'
_exptl_crystal_density_diffrn    1.088
_exptl_crystal_description       block
_exptl_crystal_F_000             11712
_exptl_crystal_size_max          0.75
_exptl_crystal_size_mid          0.66
_exptl_crystal_size_min          0.31
_platon_squeeze_details
;
TITL Mad_Mn4W2_0m_a.res in I4(1)/a
CELL   23.6740   23.6740   63.0580     90.00     90.00     90.00
SPGR I41/a
Q101 0.589 0.544 0.125 !       6.74 eA-3
Q102 0.616 0.167 0.124 !       6.50 eA-3
Q103 0.804 0.358 0.126 !       6.33 eA-3
Q104 0.594 0.140 0.110 !       5.61 eA-3
Q105 0.405 0.329 0.124 !       5.55 eA-3
Q106 0.998 0.121 0.121 !       5.10 eA-3
C107 0.508 0.809 0.131 !       4.73 eA-3
C108 0.079 0.041 0.081 !       4.70 eA-3
Q109 0.203 0.378 0.117 !       4.39 eA-3
Q110 0.421 0.565 0.117 !       4.27 eA-3
C111 0.789 0.173 0.077 !       3.85 eA-3
C112 0.735 0.184 0.183 !       3.39 eA-3
Q113 0.625 0.529 0.172 !       3.09 eA-3
C114 0.297 0.860 0.080 !       3.01 eA-3
C115 0.515 0.957 0.081 !       2.98 eA-3
C116 0.063 0.258 0.170 !       2.96 eA-3
C117 0.563 0.758 0.670 !       2.96 eA-3
Q118 0.288 0.799 0.167 !       2.91 eA-3
C119 0.998 0.313 0.166 !       2.88 eA-3
Q120 0.178 0.963 0.129 !       2.88 eA-3
C121 0.638 0.738 0.167 !       2.75 eA-3
Q122 0.108 0.681 0.078 !       2.63 eA-3
C123 0.930 0.740 0.837 !       2.60 eA-3
Q124 0.798 0.167 0.128 !       2.60 eA-3
Q125 0.601 0.241 0.144 !       2.59 eA-3
C126 0.736 0.166 0.053 !       2.57 eA-3
Q127 0.580 0.171 0.174 !       2.55 eA-3
C128 0.991 0.196 0.057 !       2.51 eA-3
C129 0.245 0.771 0.184 !       2.49 eA-3
C130 0.799 0.198 0.072 !       2.46 eA-3
C131 0.006 0.126 0.079 !       2.38 eA-3
Q132 0.928 0.126 0.104 !       2.37 eA-3
C133 0.501 0.865 0.179 !       2.37 eA-3
C134 0.540 0.659 0.161 !       2.36 eA-3
C135 0.791 0.066 0.027 !       2.36 eA-3
Q136 0.302 0.333 0.200 !       2.35 eA-3
C137 0.941 0.352 0.079 !       2.35 eA-3
Q138 0.396 0.552 0.083 !       2.35 eA-3
Q139 0.633 0.350 0.118 !       2.34 eA-3
C140 0.219 0.978 0.032 !       2.34 eA-3
C141 0.889 0.259 0.152 !       2.32 eA-3
C142 0.078 0.264 0.129 !       2.32 eA-3
C143 0.346 0.782 0.153 !       2.31 eA-3
Q144 0.352 0.954 0.117 !       2.31 eA-3
Q145 0.616 0.937 0.130 !       2.30 eA-3
C146 0.507 0.857 0.598 !       2.30 eA-3
Q147 0.786 0.133 0.149 !       2.28 eA-3
C148 0.553 0.895 0.090 !       2.27 eA-3
Q149 0.258 0.797 0.174 !       2.27 eA-3
C150 0.486 0.761 0.201 !       2.23 eA-3
C151 0.467 0.653 0.102 !       2.22 eA-3
Q152 0.102 0.452 0.168 !       2.22 eA-3
C153 0.688 0.724 0.186 !       2.19 eA-3
C154 0.592 0.548 0.079 !       2.19 eA-3
Q155 0.682 0.466 0.118 !       2.18 eA-3
C156 0.923 0.334 0.102 !       2.17 eA-3
Q157 0.872 0.106 0.121 !       2.16 eA-3
Q158 0.927 0.841 0.134 !       2.16 eA-3
C159 0.353 0.816 0.128 !       2.16 eA-3
Q160 0.755 0.217 0.062 !       2.15 eA-3
C161 0.201 0.602 0.005 !       2.15 eA-3
Q162 0.437 0.500 0.180 !       2.15 eA-3
Q163 0.439 0.876 0.125 !       2.14 eA-3
C164 0.414 0.482 0.208 !       2.14 eA-3
Q165 0.824 0.528 0.191 !       2.14 eA-3
C166 0.281 0.744 0.186 !       2.13 eA-3
Q167 0.195 0.392 0.177 !       2.13 eA-3
Q168 0.688 0.702 0.120 !       2.13 eA-3
C169 0.229 0.976 0.023 !       2.11 eA-3
Q170 0.618 0.973 0.120 !       2.11 eA-3
Q171 0.220 0.899 0.108 !       2.11 eA-3
C172 0.016 0.238 0.114 !       2.09 eA-3
C173 0.773 0.756 0.020 !       2.08 eA-3
Q174 0.500 0.755 0.027 !       2.08 eA-3
Q175 0.118 0.967 0.181 !       2.08 eA-3
C176 0.204 0.804 0.008 !       2.07 eA-3
C177 0.854 0.487 0.206 !       2.07 eA-3
Q178 0.133 0.283 0.098 !       2.06 eA-3
C179 0.928 0.165 0.155 !       2.06 eA-3
C180 0.750 0.199 0.079 !       2.06 eA-3
C181 0.973 0.419 0.098 !       2.06 eA-3
Q182 0.398 0.121 0.168 !       2.06 eA-3
C183 0.869 0.503 0.203 !       2.05 eA-3
C184 0.767 0.533 0.215 !       2.05 eA-3
Q185 0.362 0.477 0.188 !       2.05 eA-3
C186 0.572 0.967 0.192 !       2.05 eA-3
C187 0.039 0.185 0.175 !       2.04 eA-3
C188 0.503 0.867 0.606 !       2.03 eA-3
C189 0.459 0.555 0.165 !       2.03 eA-3
Q190 0.031 0.119 0.621 !       2.02 eA-3
Q191 0.969 0.881 0.379 !       2.02 eA-3
Q192 0.531 0.619 0.121 !       2.02 eA-3
C193 0.761 0.117 0.032 !       2.02 eA-3
C194 0.991 0.181 0.103 !       2.02 eA-3
C195 0.425 0.620 0.105 !       2.02 eA-3
C196 0.196 0.018 0.214 !       2.01 eA-3
C197 0.750 0.697 0.054 !       2.01 eA-3
Q198 0.843 0.064 0.058 !       1.99 eA-3
Q199 0.632 0.889 0.197 !       1.98 eA-3
;
_refine_diff_density_max         3.559
_refine_diff_density_min         -2.999
_refine_diff_density_rms         0.246
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.087
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     789
_refine_ls_number_reflns         18203
_refine_ls_number_restraints     770
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.1584
_refine_ls_R_factor_gt           0.1455
_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^)+(0.0851P)^2^+2917.1599P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3391
_refine_ls_wR_factor_ref         0.3492
_reflns_Friedel_coverage         0.000
_reflns_number_gt                16464
_reflns_number_total             18203
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b09576_si_011.cif
_cod_data_source_block           mad_mn4w2_0m_a_sq
_cod_original_cell_volume        35341(5)
_cod_original_sg_symbol_H-M      'I 41/a'
_cod_database_code               4129188
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.633
_shelx_estimated_absorpt_t_min   0.376
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.737(2)
 0.263(2)
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
 C30-C29
 1.45 with sigma of 0.02
 C69-C58
 1.5 with sigma of 0.02
 C68-C56
 2.44 with sigma of 0.02
 C68-C58
 2.44 with sigma of 0.02
 C68-C57
 1.45 with sigma of 0.01
 C31-C30
 1.45 with sigma of 0.02
 C39-C34
 1.55 with sigma of 0.02
 C59-C61
 1.39 with sigma of 0.02
 C29-C30
 1.39 with sigma of 0.02
 C30-C31
 1.39 with sigma of 0.02
 C61-C59
 1.39 with sigma of 0.02
 C21-C11
 1.45 with sigma of 0.01
 C20-C10
 1.45 with sigma of 0.01
 N9-C13
 1.39 with sigma of 0.02
 C0BA-C13
 1.39 with sigma of 0.02
 C12-C13
 1.39 with sigma of 0.02
 C14-C12
 1.39 with sigma of 0.02
 C18-C19
 1.45 with sigma of 0.02
 C23-C18
 1.45 with sigma of 0.02
 C14-C15
 1.39 with sigma of 0.02
 C15-C16
 1.39 with sigma of 0.02
 C22-C17
 1.45 with sigma of 0.02
 C60-C64
 1.39 with sigma of 0.02
 C61-C62
 1.39 with sigma of 0.02
 C62-C63
 1.39 with sigma of 0.02
 C47-C46
 1.39 with sigma of 0.02
 C45-C46
 1.39 with sigma of 0.02
 C45-C43
 1.39 with sigma of 0.02
 C48-C44
 1.39 with sigma of 0.02
 C41-C52
 1.45 with sigma of 0.02
 C55-C50
 1.5 with sigma of 0.02
 C70-C65
 1.45 with sigma of 0.01
 C38-C33
 1.45 with sigma of 0.01
 C27-C29
 1.39 with sigma of 0.02
 C32-C28
 1.39 with sigma of 0.02
 C37-C26
 1.45 with sigma of 0.02
 C39-C33
 2.44 with sigma of 0.04
 C39-C35
 2.44 with sigma of 0.04
 C11-C20 = C33-C39
 2.6 with sigma of 0.04
 C23-C19
 2.44 with sigma of 0.04
 C23-C17
 2.44 with sigma of 0.04
 C71-C65
 2.51 with sigma of 0.04
4. Restrained planarity
 C17, C18, C19, C23, C22, C16, C0BA, C13, C12, C14, C15, C11, C21, C10, C20,
 C9, N9, N10
 with sigma of 0.1
 C40, C41, C46, C45, C47, C50, C43, C49, C42, C51, C55, C52, C48, C53, C44, C54
 with sigma of 0.01
 C69, C61, C56, C57, C58, C59, C60, C68, C65, C66, C67, C64, C63, C71, C62, C70
 with sigma of 0.01
 C35, N12, C32, C31, C33, C34, C38, C37, C24, N11, C28, C27, C26, C25, C29,
 C30, C36, C39
 with sigma of 0.01
5. Uiso/Uaniso restraints and constraints
C34 \\sim C39: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
C21 \\sim C11: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
C20 \\sim C10: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
C23 \\sim C18 \\sim C19 \\sim N10 \\sim C0BA \\sim C16 \\sim C17 \\sim C22
\\sim C15 \\sim C14 \\sim C12 \\sim C13 \\sim N9 \\sim C9 \\sim C10 \\sim C20
\\sim C11 \\sim C21: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02
C23 \\sim C18: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002
C66 \\sim C71: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
N5 \\sim C5: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
N2 \\sim C2: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
N3 \\sim C3: 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
C40 \\sim C41 \\sim C46 \\sim C45 \\sim C47 \\sim C50 \\sim C43 \\sim C49 \\sim
C42 \\sim C51 \\sim C55 \\sim C52 \\sim C48 \\sim C53 \\sim C44 \\sim C54:
within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
C69 \\sim C61 \\sim N15 \\sim C56 \\sim C57 \\sim C58 \\sim C59 \\sim C60 \\sim
C68 \\sim C65 \\sim C66 \\sim C67 \\sim C64 \\sim C63 \\sim C71 \\sim C62 \\sim
C70: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
N6 \\sim C6: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C7 \\sim N7: within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08
C8 \\sim N8: within 2A with sigma of 0.02 and sigma for terminal atoms of 0.04
C4 \\sim N4: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C35 \\sim N12 \\sim N12 \\sim C32 \\sim C31 \\sim C33 \\sim C34 \\sim C71 \\sim
C38 \\sim C37 \\sim C24 \\sim N11 \\sim N11 \\sim C28 \\sim C27 \\sim C26 \\sim
C25 \\sim C29 \\sim C30 \\sim C36: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.03
Uanis(C69) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C58) \\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C71) \\sim Ueq: with sigma of
0.1 and sigma for terminal atoms of 0.2
Uanis(C60) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C35) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C32) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(N10) \\sim Ueq: with sigma of 0.04 and sigma for terminal atoms of 0.08
Uanis(C2) \\sim Ueq: with sigma of 0.0001 and sigma for terminal atoms of 0.0002
Uanis(C3) \\sim Ueq, Uanis(N3) \\sim Ueq: with sigma of 0.0001 and sigma for
terminal atoms of 0.0002
Uanis(N2) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C5) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C1) \\sim Ueq, Uanis(N1) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(N1) \\sim Ueq, Uanis(C1) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C52) \\sim Ueq: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C51) \\sim Ueq, Uanis(C52) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C70) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C6) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C7) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C8) \\sim Ueq, Uanis(N8) \\sim Ueq: with sigma of 0.02 and sigma for
terminal atoms of 0.04
Uanis(N4) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C4) \\sim Ueq, Uanis(N4) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C25) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(N11) \\sim Ueq, Uanis(C26)
\\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
6.a Aromatic/amide H refined with riding coordinates:
 C19(H19), C61(H61), C40(H40), C56(H56), C46(H46), C45(H45), C67(H67),
 C51(H51), C35(H35), C62(H62), C9(H9), C24(H24), C29(H29), C30(H30), C14(H14),
 C15(H15)
6.b Fitted hexagon refined as free rotating group:
 N15(C56,C57,C58,C59,C60), C65(C66,C67,N16,C64,C63), C35(N12,C32,C31,C33,C34),
 C24(N11,C28,C27,C26,C25)
6.c Idealised Me refined as rotating group:
 C69(H69A,H69B,H69C), C68(H68A,H68B,H68C), C22(H22A,H22B,H22C), C21(H21A,H21B,
 H21C), C55(H55A,H55B,H55C), C52(H52A,H52B,H52C), C71(H71A,H71B,H71C), C38(H38A,
 H38B,H38C), C37(H37A,H37B,H37C), C20(H20A,H20B,H20C), C53(H53A,H53B,H53C),
 C54(H54A,H54B,H54C), C36(H36A,H36B,H36C), C39(H39A,H39B,H39C), C70(H70A,H70B,
 H70C), C23(H23A,H23B,H23C)
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'