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_1571623
_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         'C32 H16 Au4 Fe2 N16 O2, 2(C16 H10)'
_chemical_formula_sum            'C64 H36 Au4 Fe2 N16 O2'
_chemical_formula_weight         1960.65
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2024-04-25
_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            8
_cell_length_a                   27.6016(6)
_cell_length_b                   28.7074(8)
_cell_length_c                   15.3460(5)
_cell_measurement_reflns_used    5509
_cell_measurement_temperature    202.99(10)
_cell_measurement_theta_max      27.3720
_cell_measurement_theta_min      2.9010
_cell_volume                     12159.7(6)
_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    'SHELXS-1997  (Sheldrick, 2008)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      202.99(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   -110.00 -85.00   1.00   10.00    --    0.27-178.00 -30.00   25
  2  \w     82.00 107.00   1.00   10.00    --    0.27 178.00 -90.00   25
  3  \w     49.00  74.00   1.00   10.00    --    0.27 178.00 -90.00   25
  4  \w     95.00 132.00   1.00   10.00    --   30.06  77.00-150.00   37
  5  \w    -25.00  14.00   1.00   10.00    --   30.06  77.00-180.00   39
  6  \w     20.00 132.00   1.00   10.00    --   30.06  57.00 -30.00  112
;
_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      -0.0056004000
_diffrn_orient_matrix_UB_12      -0.0088962000
_diffrn_orient_matrix_UB_13      -0.0419355000
_diffrn_orient_matrix_UB_21      0.0216921000
_diffrn_orient_matrix_UB_22      0.0097797000
_diffrn_orient_matrix_UB_23      -0.0166832000
_diffrn_orient_matrix_UB_31      0.0125628000
_diffrn_orient_matrix_UB_32      -0.0208720000
_diffrn_orient_matrix_UB_33      0.0100841000
_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  0.0648
_diffrn_reflns_av_unetI/netI     0.0834
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -32
_diffrn_reflns_limit_k_max       34
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            30012
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.000
_diffrn_reflns_theta_max         25.000
_diffrn_reflns_theta_min         2.440
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    10.140
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.14045
_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    2.142
_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         2.906
_refine_diff_density_min         -3.523
_refine_diff_density_rms         0.245
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.163
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     905
_refine_ls_number_reflns         10693
_refine_ls_number_restraints     516
_refine_ls_restrained_S_all      1.141
_refine_ls_R_factor_all          0.1351
_refine_ls_R_factor_gt           0.0899
_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^)+(0.0346P)^2^+305.3633P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1755
_refine_ls_wR_factor_ref         0.1985
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6892
_reflns_number_total             10693
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00331d2.cif
_cod_data_source_block           1_203k
_cod_depositor_comments
'Adding full bibliography for 1571621--1571630.cif.'
_cod_database_code               1571623
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         FeAuCNO
_shelx_estimated_absorpt_t_max   0.352
_shelx_estimated_absorpt_t_min   0.263
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C61-C60 \\sim C51A-C50A
 with sigma of 0.02
 C61-C52 \\sim C51A-C52A
 with sigma of 0.02
 C61-C62 \\sim C51A-C64A
 with sigma of 0.02
 C50-C49 \\sim C60A-C59A
 with sigma of 0.02
 C50-C51 \\sim C60A-C61A
 with sigma of 0.02
 C60-C59 \\sim C50A-C49A
 with sigma of 0.02
 C52-C51 \\sim C52A-C61A
 with sigma of 0.02
 C52-C53 \\sim C52A-C53A
 with sigma of 0.02
 C59-C58 \\sim C49A-C54A
 with sigma of 0.02
 C49-C54 \\sim C59A-C58A
 with sigma of 0.02
 C62-C63 \\sim C64A-C63A
 with sigma of 0.02
 C64-C51 \\sim C62A-C61A
 with sigma of 0.02
 C64-C63 \\sim C62A-C63A
 with sigma of 0.02
 C55-C54 \\sim C57A-C58A
 with sigma of 0.02
 C55-C56 \\sim C57A-C56A
 with sigma of 0.02
 C54-C53 \\sim C58A-C53A
 with sigma of 0.02
 C53-C58 \\sim C53A-C54A
 with sigma of 0.02
 C58-C57 \\sim C54A-C55A
 with sigma of 0.02
 C57-C56 \\sim C55A-C56A
 with sigma of 0.02
 C61-C59 \\sim C51A-C49A
 with sigma of 0.04
 C61-C51 \\sim C51A-C61A
 with sigma of 0.04
 C61-C53 \\sim C51A-C53A
 with sigma of 0.04
 C61-C63 \\sim C51A-C63A
 with sigma of 0.04
 C50-C52 \\sim C60A-C52A
 with sigma of 0.04
 C50-C64 \\sim C60A-C62A
 with sigma of 0.04
 C50-C54 \\sim C60A-C58A
 with sigma of 0.04
 C60-C52 \\sim C50A-C52A
 with sigma of 0.04
 C60-C62 \\sim C50A-C64A
 with sigma of 0.04
 C60-C58 \\sim C50A-C54A
 with sigma of 0.04
 C52-C62 \\sim C52A-C64A
 with sigma of 0.04
 C52-C64 \\sim C52A-C62A
 with sigma of 0.04
 C52-C54 \\sim C52A-C58A
 with sigma of 0.04
 C52-C58 \\sim C52A-C54A
 with sigma of 0.04
 C59-C53 \\sim C49A-C53A
 with sigma of 0.04
 C59-C57 \\sim C49A-C55A
 with sigma of 0.04
 C49-C51 \\sim C59A-C61A
 with sigma of 0.04
 C49-C55 \\sim C59A-C57A
 with sigma of 0.04
 C49-C53 \\sim C59A-C53A
 with sigma of 0.04
 C62-C64 \\sim C64A-C62A
 with sigma of 0.04
 C51-C53 \\sim C61A-C53A
 with sigma of 0.04
 C51-C63 \\sim C61A-C63A
 with sigma of 0.04
 C55-C53 \\sim C57A-C53A
 with sigma of 0.04
 C55-C57 \\sim C57A-C55A
 with sigma of 0.04
 C54-C58 \\sim C58A-C54A
 with sigma of 0.04
 C54-C56 \\sim C58A-C56A
 with sigma of 0.04
 C53-C57 \\sim C53A-C55A
 with sigma of 0.04
 C58-C56 \\sim C54A-C56A
 with sigma of 0.04
 C58-C57 \\sim C57-C56
 with sigma of 0.02
3. Rigid bond restraints
 C57, C61, C60, C52, C62, H60, C59, C51, C53, H62, C63, H59, C58, C50, C64,
 C54, H63, H50, C49, H64, C55, H57, C56, H49, H55, H56, C64A, C59A, H59A, C60A,
 C58A, C61A, H60A, C57A, C53A, C52A, C62A, H57A, C56A, C54A, C51A, C63A, H62A,
 C55A, H56A, C49A, C50A, H63A, H55A, H49A, H50A, H64A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C47, C37, C38, C36, C42, C33, C39, C48, C35, C43, C41, H33, C34, C40, H39,
 H48, H35, C46, C44, H34, H40, H47, H46, C45, H44, H45
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
Uanis(C61) \\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C51)
\\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C58) \\sim Ueq, Uanis(C63) \\sim Ueq,
Uanis(C50) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C49)
\\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C56) \\sim Ueq,
Uanis(C52) \\sim Ueq, Uanis(C64) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C59A) \\sim Ueq, Uanis(C62A) \\sim Ueq, Uanis(C54A) \\sim Ueq,
Uanis(C60A) \\sim Ueq, Uanis(C58A) \\sim Ueq, Uanis(C53A) \\sim Ueq,
Uanis(C56A) \\sim Ueq, Uanis(C51A) \\sim Ueq, Uanis(C64A) \\sim Ueq,
Uanis(C57A) \\sim Ueq, Uanis(C49A) \\sim Ueq, Uanis(C50A) \\sim Ueq,
Uanis(C61A) \\sim Ueq, Uanis(C55A) \\sim Ueq, Uanis(C52A) \\sim Ueq,
Uanis(C63A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C34) \\sim Ueq, Uanis(C37) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(C36)
\\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C39) \\sim Ueq,
Uanis(C48) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C41)
\\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C46) \\sim Ueq,
Uanis(C44) \\sim Ueq, Uanis(C45) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C24) \\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(C5) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C8) \\sim Ueq, Uanis(C26) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C51A) \\sim Ueq, Uanis(C62A) \\sim Ueq, Uanis(C56) \\sim Ueq, Uanis(Au3)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
5. Others
 Sof(C59A)=Sof(H59A)=Sof(C51A)=Sof(C50A)=Sof(H50A)=Sof(C52A)=Sof(C64A)=
 Sof(H64A)=Sof(C49A)=Sof(H49A)=Sof(C61A)=Sof(C63A)=Sof(H63A)=Sof(C60A)=
 Sof(H60A)=Sof(C62A)=Sof(H62A)=Sof(C57A)=Sof(H57A)=Sof(C58A)=Sof(C53A)=
 Sof(C54A)=Sof(C55A)=Sof(H55A)=Sof(C56A)=Sof(H56A)=1-FVAR(1)
 Sof(C61)=Sof(C50)=Sof(H50)=Sof(C60)=Sof(H60)=Sof(C52)=Sof(C59)=Sof(H59)=
 Sof(C49)=Sof(H49)=Sof(C62)=Sof(H62)=Sof(C64)=Sof(H64)=Sof(C51)=Sof(C55)=
 Sof(H55)=Sof(C54)=Sof(C53)=Sof(C58)=Sof(C57)=Sof(H57)=Sof(C56)=Sof(H56)=
 Sof(C63)=Sof(H63)=FVAR(1)
6.a Aromatic/amide H refined with riding coordinates:
 C29(H29), C11(H11), C32(H32), C21(H21), C31(H31), C2(H2), C5(H5), C22(H22),
 C1(H1), C48(H48), C9(H9), C46(H46), C25(H25), C30(H30), C24(H24), C34(H34),
 C12(H12), C10(H10), C4(H4), C47(H47), C33(H33), C40(H40), C39(H39), C44(H44),
 C45(H45), C35(H35), C50(H50), C60(H60), C59(H59), C49(H49), C62(H62), C64(H64),
  C55(H55), C57(H57), C56(H56), C63(H63), C59A(H59A), C50A(H50A), C64A(H64A),
 C49A(H49A), C63A(H63A), C60A(H60A), C62A(H62A), C57A(H57A), C55A(H55A),
 C56A(H56A)
6.b Fitted pentagon refined as free rotating group:
 N14(C26,O2,C27,N15)
6.c Fitted hexagon refined as free rotating group:
 C55(C54,C53,C58,C57,C56), C57A(C58A,C53A,C54A,C55A,C56A)
;
_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 4.332
_oxdiff_exptl_absorpt_empirical_full_min 0.637