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_1571628
_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     iterative
_audit_creation_date             2024-05-01
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-05-01 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                   15.0987(8)
_cell_length_b                   27.5674(15)
_cell_length_c                   28.4870(15)
_cell_measurement_reflns_used    9775
_cell_measurement_temperature    145.00
_cell_measurement_theta_max      27.593
_cell_measurement_theta_min      2.329
_cell_volume                     11857.2(11)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      145.00
_diffrn_detector                 'Bruker APEX2 area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker SMART APEX2 area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0763
_diffrn_reflns_av_unetI/netI     0.0517
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       17
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       33
_diffrn_reflns_limit_l_min       -33
_diffrn_reflns_number            158321
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        24.999
_diffrn_reflns_theta_max         24.999
_diffrn_reflns_theta_min         1.526
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_exptl_absorpt_coefficient_mu    10.398
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.5417
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1198 before and 0.0836 after correction.
The Ratio of minimum to maximum transmission is 0.7265.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'clear reddish red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   reddish
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    2.197
_exptl_crystal_description       block
_exptl_crystal_F_000             7328
_exptl_crystal_size_max          0.138
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.076
_refine_diff_density_max         2.006
_refine_diff_density_min         -0.907
_refine_diff_density_rms         0.206
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.417(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.045
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1562
_refine_ls_number_reflns         20860
_refine_ls_number_restraints     800
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0439
_refine_ls_R_factor_gt           0.0328
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0117P)^2^+19.1471P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0624
_refine_ls_wR_factor_ref         0.0649
_reflns_Friedel_coverage         0.844
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                17919
_reflns_number_total             20860
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00331d2.cif
_cod_data_source_block           1_145k
_cod_depositor_comments
'Adding full bibliography for 1571621--1571630.cif.'
_cod_database_code               1571628
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.505
_shelx_estimated_absorpt_t_min   0.328
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.583(7)
 0.417(7)
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
 C127, C118, C119, C117, C113, C120, H119, C122, C116, H113, C114, H120, C121,
 C123, C115, C128, H114, C126, C124, H115, H128, C125, H126, H124, H127, H125
 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'