Bidirectional photomagnetism, exciplex fluorescence and dielectric anomalies in a spin crossover Hofmann-type coordination polymer.
Chen, Yan-Ru; Ying, Ting-Ting; Chen, Yan-Cong; Liao, Pei-Yu; Ni, Zhao-Ping; Tong, Ming-Liang; Chemical science 15 (2024) 9240–9248; doi:10.1039/d4sc00331d

data_1571624
_publ_section_title
;
 Bidirectional photomagnetism, exciplex fluorescence and dielectric
 anomalies in a spin crossover Hofmann-type coordination polymer.
;
_journal_issue                   24
_journal_name_full               'Chemical science'
_journal_page_first              9240
_journal_page_last               9248
_journal_paper_doi               10.1039/d4sc00331d
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C64 H32 Au8 Fe4 N32 O4, 4(C16 H10)'
_chemical_formula_sum            'C128 H72 Au8 Fe4 N32 O4'
_chemical_formula_weight         3921.30
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-04-03
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-04-05 deposited with the CCDC.	2024-05-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.2903(10)
_cell_length_b                   27.605(2)
_cell_length_c                   28.6786(16)
_cell_measurement_reflns_used    5204
_cell_measurement_temperature    197.99(10)
_cell_measurement_theta_max      27.8430
_cell_measurement_theta_min      2.8530
_cell_volume                     12104.9(14)
_computing_cell_refinement       'CrysAlisPro 1.171.42.92a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.92a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.92a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      197.99(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 5.2913
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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    -13.00  14.00   1.00   10.00    --  -14.02 -77.00  90.00   27
  2  \w     -9.00  80.00   1.00   10.00    --   14.80  38.00   0.00   89
  3  \w     -5.00  35.00   1.00   10.00    --   14.80  19.00 -30.00   40
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0158618000
_diffrn_orient_matrix_UB_12      0.0240551000
_diffrn_orient_matrix_UB_13      0.0021624000
_diffrn_orient_matrix_UB_21      -0.0435369000
_diffrn_orient_matrix_UB_22      -0.0088541000
_diffrn_orient_matrix_UB_23      0.0003675000
_diffrn_orient_matrix_UB_31      0.0020302000
_diffrn_orient_matrix_UB_32      -0.0019378000
_diffrn_orient_matrix_UB_33      0.0246282000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0579
_diffrn_reflns_av_unetI/netI     0.0935
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            40681
_diffrn_reflns_point_group_measured_fraction_full 0.968
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         2.513
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    10.185
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.53533
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.92a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    2.152
_exptl_crystal_description       block
_exptl_crystal_F_000             7328
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.17
_exptl_crystal_size_min          0.13
_refine_diff_density_max         1.940
_refine_diff_density_min         -2.747
_refine_diff_density_rms         0.229
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.48(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1562
_refine_ls_number_reflns         20643
_refine_ls_number_restraints     753
_refine_ls_restrained_S_all      1.053
_refine_ls_R_factor_all          0.1095
_refine_ls_R_factor_gt           0.0698
_refine_ls_shift/su_max          0.001
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0379P)^2^+79.8754P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1392
_refine_ls_wR_factor_ref         0.1636
_reflns_Friedel_coverage         0.790
_reflns_Friedel_fraction_full    0.933
_reflns_Friedel_fraction_max     0.933
_reflns_number_gt                14210
_reflns_number_total             20643
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00331d2.cif
_cod_data_source_block           1_198K
_cod_depositor_comments
'Adding full bibliography for 1571621--1571630.cif.'
_cod_original_cell_volume        12105.1(14)
_cod_database_code               1571624
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         FeAuCNOH
_chemical_oxdiff_usercomment     FeAuCNOH
_shelx_estimated_absorpt_t_max   0.351
_shelx_estimated_absorpt_t_min   0.261
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.52(2)
 0.48(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
3. Restrained distances
 C94-C93 \\sim C84-C83 \\sim C96-C95 \\sim C90-C89 \\sim C88-C87 \\sim C86-C85
 with sigma of 0.02
 C86-C81 \\sim C82-C83
 with sigma of 0.02
4. Rigid bond restraints
 C96, C92, H92, C91, C93, H91, C90, C94, C84, C89, C85, H94, C95, C83, H89,
 C88, C86, H95, C82, H88, C87, C81, H96, H82, H87, H81
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
Uanis(C80) \\sim Ueq, Uanis(C69) \\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C74)
\\sim Ueq, Uanis(C68) \\sim Ueq, Uanis(C65) \\sim Ueq, Uanis(C71) \\sim Ueq,
Uanis(C73) \\sim Ueq, Uanis(C75) \\sim Ueq, Uanis(C77) \\sim Ueq, Uanis(C67)
\\sim Ueq, Uanis(C66) \\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C76) \\sim Ueq,
Uanis(C78) \\sim Ueq, Uanis(C79) \\sim Ueq, Uanis(C97) \\sim Ueq, Uanis(C101)
\\sim Ueq, Uanis(C106) \\sim Ueq, Uanis(C102) \\sim Ueq, Uanis(C100) \\sim Ueq,
Uanis(C105) \\sim Ueq, Uanis(C107) \\sim Ueq, Uanis(C103) \\sim Ueq, Uanis(C99)
\\sim Ueq, Uanis(C109) \\sim Ueq, Uanis(C104) \\sim Ueq, Uanis(C108) \\sim Ueq,
Uanis(C98) \\sim Ueq, Uanis(C112) \\sim Ueq, Uanis(C110) \\sim Ueq, Uanis(C111)
\\sim Ueq, Uanis(C114) \\sim Ueq, Uanis(C118) \\sim Ueq, Uanis(C119) \\sim Ueq,
Uanis(C117) \\sim Ueq, Uanis(C113) \\sim Ueq, Uanis(C120) \\sim Ueq,
Uanis(C122) \\sim Ueq, Uanis(C116) \\sim Ueq, Uanis(C121) \\sim Ueq,
Uanis(C123) \\sim Ueq, Uanis(C115) \\sim Ueq, Uanis(C128) \\sim Ueq,
Uanis(C126) \\sim Ueq, Uanis(C124) \\sim Ueq, Uanis(C127) \\sim Ueq,
Uanis(C125) \\sim Ueq, Uanis(C88) \\sim Ueq, Uanis(C86) \\sim Ueq, Uanis(C85)
\\sim Ueq, Uanis(C81) \\sim Ueq, Uanis(C87) \\sim Ueq, Uanis(C90) \\sim Ueq,
Uanis(C83) \\sim Ueq, Uanis(C84) \\sim Ueq, Uanis(C82) \\sim Ueq, Uanis(C89)
\\sim Ueq, Uanis(C91) \\sim Ueq, Uanis(C92) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C43) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C21)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C95) \\sim Ueq, Uanis(C96) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(N1) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C93) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C15) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C13)
\\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C25) \\sim Ueq, Uanis(C1) \\sim Ueq,
Uanis(C5) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(N11) \\sim
Ueq, Uanis(C28) \\sim Ueq, Uanis(N18) \\sim Ueq, Uanis(C42) \\sim Ueq,
Uanis(N26) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C60)
\\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(N21) \\sim Ueq, Uanis(C49) \\sim Ueq,
Uanis(C48) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C54)
\\sim Ueq, Uanis(C40) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
Uanis(C94) \\sim Ueq, Uanis(C85) \\sim Ueq, Uanis(N25) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(N6) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C26) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C72) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(N19) \\sim Ueq, Uanis(N17) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(N32) \\sim Ueq, Uanis(N4) \\sim Ueq, Uanis(N14) \\sim Ueq, Uanis(N15)
\\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(N9) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C58) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C46)
\\sim Ueq, Uanis(C101) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C29) \\sim Ueq,
Uanis(C32) \\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(C38) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
6.a Aromatic/amide H refined with riding coordinates:
 C17(H17), C29(H29), C2(H2), C54(H54), C10(H10), C1(H1), C53(H53), C5(H5),
 C24(H24), C30(H30), C33(H33), C32(H32), C4(H4), C9(H9), C16(H16), C23(H23),
 C13(H13), C49(H49), C45(H45), C56(H56), C46(H46), C14(H14), C55(H55), C12(H12),
  C65(H65), C103(H103), C22(H22), C48(H48), C66(H66), C105(H105), C11(H11),
 C76(H76), C21(H21), C104(H104), C97(H97), C98(H98), C111(H111), C112(H112),
 C110(H110), C73(H73), C71(H71), C72(H72), C75(H75), C79(H79), C78(H78),
 C92(H92), C91(H91), C120(H120), C119(H119), C125(H125), C124(H124), C113(H113),
  C115(H115), C107(H107), C127(H127), C114(H114), C126(H126), C108(H108),
 C128(H128), C80(H80), C89(H89), C88(H88), C87(H87), C82(H82), C81(H81),
 C39(H39), C37(H37), C38(H38), C40(H40), C94(H94), C96(H96), C95(H95)
6.b Fitted hexagon refined as free rotating group:
 C90(C89,C88,C87,C86,C85), C94(C93,C84,C83,C96,C95)
;
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.624
_oxdiff_exptl_absorpt_empirical_full_min 0.784