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_1571627
_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 N16 O2 Zn2, 2(C16 H10)'
_chemical_formula_sum            'C64 H36 Au4 N16 O2 Zn2'
_chemical_formula_weight         1979.69
_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
_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            8
_cell_length_a                   15.40179(12)
_cell_length_b                   27.7406(2)
_cell_length_c                   28.6941(2)
_cell_measurement_reflns_used    53196
_cell_measurement_temperature    198.00(10)
_cell_measurement_theta_max      76.8990
_cell_measurement_theta_min      3.0700
_cell_volume                     12259.69(16)
_computing_cell_refinement       'CrysAlisPro 1.171.43.98a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.98a 64-bit (release 24-11-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.98a (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)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      198.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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     76.00 101.00   0.50    0.24    --  123.00 -77.00  60.00   50
  2  \w     46.00  97.00   0.50    0.24    --  123.00 -77.00  30.00  102
  3  \w     33.00  58.00   0.50    0.24    --  123.00 -77.00   0.00   50
  4  \w     64.00  90.00   0.50    0.24    --  123.00 -77.00   0.00   52
  5  \w     45.00  72.00   0.50    0.24    --  123.00 -64.00  60.00   54
  6  \w     40.00  73.00   0.50    0.24    --  123.00 -64.00 150.00   66
  7  \w     40.00  73.00   0.50    0.24    --  123.00 -64.00  30.00   66
  8  \w     47.00  72.00   0.50    0.24    --  123.00 -64.00  90.00   50
  9  \w     56.00  97.00   0.50    0.24    --  123.00 -77.00 -90.00   82
 10  \w     40.00  69.00   0.50    0.24    --  123.00 -64.00 -90.00   58
 11  \w     40.00  65.00   0.50    0.24    --  123.00 -64.00-150.00   50
 12  \w     75.00 100.00   0.50    0.24    --  123.00 -77.00-180.00   50
 13  \w    -16.00  38.00   0.50    0.24    --   69.84 -45.00 -60.00  108
 14  \w    -16.00  35.00   0.50    0.24    --   69.84 -45.00 120.00  102
 15  \w     30.00  65.00   0.50    0.24    --  123.00 -92.00 -30.00   70
 16  \w     18.00  49.00   0.50    0.24    --   69.84-125.00-120.00   62
 17  \w     61.00 112.00   0.50    0.24    --   69.84-125.00-120.00  102
 18  \w     72.00 107.00   0.50    0.24    --  123.00-112.00-150.00   70
 19  \w     62.00 109.00   0.50    0.24    --  123.00-112.00-180.00   94
 20  \w     37.00  69.00   0.50    0.24    --  123.00-112.00-150.00   64
 21  \w     37.00 109.00   0.50    0.24    --  123.00-112.00-120.00  144
 22  \w     52.00 105.00   0.50    0.24    --  123.00-112.00 -90.00  106
 23  \w     73.00 109.00   0.50    0.24    --  123.00-112.00 -60.00   72
 24  \w     83.00 109.00   0.50    0.24    --  123.00-112.00 -30.00   52
 25  \w     83.00 109.00   0.50    0.24    --  123.00-112.00  30.00   52
 26  \w     78.00 109.00   0.50    0.24    --  123.00-112.00  90.00   62
 27  \w     59.00 109.00   0.50    0.24    --  123.00-112.00 120.00  100
 28  \w    -11.00  14.00   0.50    0.24    --   69.84 -95.00 -30.00   50
 29  \w     52.00  82.00   0.50    0.24    --   69.84 -95.00 -30.00   60
 30  \w     30.00  65.00   0.50    0.24    --  123.00 -92.00 -90.00   70
 31  \w     69.00  95.00   0.50    0.24    --  123.00 -92.00 -90.00   52
 32  \w     79.00 104.00   0.50    0.24    --  123.00 -92.00 -30.00   50
 33  \w      2.00 152.00   0.50    0.24    --   69.84  15.00  90.00  300
 34  \w    126.00 156.00   0.50    0.24    --  123.00  77.00   0.00   60
 35  \w    126.00 174.00   0.50    0.24    --  123.00  64.00  60.00   96
 36  \w     91.00 120.00   0.50    0.24    --  123.00  64.00  60.00   58
 37  \w     77.00 115.00   0.50    0.24    --  123.00  77.00   0.00   76
 38  \w    117.00 171.00   0.50    0.24    --  123.00  77.00-120.00  108
 39  \w     77.00 112.00   0.50    0.24    --  123.00  77.00-120.00   70
 40  \w     85.00 170.00   0.50    0.24    --  123.00  64.00-150.00  170
 41  \w     89.00 126.00   0.50    0.24    --  123.00  50.00 -90.00   74
 42  \w    134.00 174.00   0.50    0.24    --  123.00  50.00 -30.00   80
 43  \w    135.00 173.00   0.50    0.24    --  123.00  50.00 -90.00   76
 44  \w     60.00  95.00   0.50    0.24    --  123.00  38.00  30.00   70
 45  \w     80.00 170.00   0.50    0.24    --  123.00  25.00   0.00  180
 46  \w    115.00 175.00   0.50    0.24    --  123.00  38.00  30.00  120
 47  \w     96.00 137.00   0.50    0.24    --  123.00  64.00  90.00   82
 48  \w     84.00 116.00   0.50    0.24    --  123.00  64.00 150.00   64
 49  \w     37.00  65.00   0.50    0.24    --  123.00  25.00   0.00   56
 50  \w    145.00 175.00   0.50    0.24    --  123.00 112.00  90.00   60
 51  \w     72.00 125.00   0.50    0.24    --  123.00 179.00 120.00  106
 52  \w     42.00  83.00   0.50    0.06    --   16.67 179.00  30.00   82
 53  \w     42.00  90.00   0.50    0.06    --   16.67 179.00-120.00   96
 54  \w    114.00 142.00   0.50    0.24    --  123.00 179.00-120.00   56
 55  \w     43.00  97.00   0.50    0.24    --  123.00 179.00-120.00  108
 56  \w     89.00 140.00   0.50    0.24    --  123.00 112.00  90.00  102
 57  \w    -58.00  59.00   0.50    0.06    --  -16.67  77.00 -30.00  234
 58  \w    -28.00  53.00   0.50    0.06    --  -16.67  19.00 -90.00  162
 59  \w     25.00  63.00   0.50    0.06    --  -16.67  19.00-150.00   76
 60  \w    -43.00  -2.00   0.50    0.24    --  -69.84  45.00 -60.00   82
 61  \w    -59.00 -19.00   0.50    0.24    --  -97.00  64.00 -60.00   80
 62  \w    -83.00 -17.00   0.50    0.24    --  -97.00  77.00  60.00  132
 63  \w    -56.00 -30.00   0.50    0.24    --  -97.00  50.00 120.00   52
 64  \w    -41.00 -15.00   0.50    0.24    --  -97.00  38.00 150.00   52
 65  \w    -37.00   6.00   0.50    0.24    --  -69.84  30.00 120.00   86
 66  \w    -14.00  12.00   0.50    0.24    --  -69.84  15.00 150.00   52
 67  \w    -45.00 -14.00   0.50    0.24    --  -97.00  38.00  60.00   62
 68  \w    -26.00  13.00   0.50    0.24    --  -69.84  15.00-180.00   78
 69  \w    -24.00   6.00   0.50    0.24    --  -69.84  15.00-120.00   60
 70  \w    -27.00   5.00   0.50    0.24    --  -69.84  15.00 -90.00   64
 71  \w    -91.00 -28.00   0.50    0.24    --  -97.00 112.00 120.00  126
 72  \w   -151.00-106.00   0.50    0.24    --  -69.84-125.00  90.00   90
 73  \w    -98.00 -48.00   0.50    0.06    --  -16.67-179.00  30.00  100
 74  \w   -147.00-112.00   0.50    0.24    --  -69.84-125.00 -60.00   70
 75  \w   -152.00 -88.00   0.50    0.24    --  -69.84-125.00-150.00  128
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0636783000
_diffrn_orient_matrix_UB_12      -0.0423876000
_diffrn_orient_matrix_UB_13      -0.0059859000
_diffrn_orient_matrix_UB_21      -0.0717079000
_diffrn_orient_matrix_UB_22      -0.0295427000
_diffrn_orient_matrix_UB_23      -0.0241683000
_diffrn_orient_matrix_UB_31      0.0284579000
_diffrn_orient_matrix_UB_32      0.0203557000
_diffrn_orient_matrix_UB_33      -0.0475637000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0641
_diffrn_reflns_av_unetI/netI     0.0273
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            123313
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        66.600
_diffrn_reflns_theta_max         66.600
_diffrn_reflns_theta_min         3.080
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    18.880
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.39809
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.98a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_density_diffrn    2.145
_exptl_crystal_description       block
_exptl_crystal_F_000             7392
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.468
_refine_diff_density_min         -1.859
_refine_diff_density_rms         0.118
_refine_ls_extinction_coef       0.0000068(5)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.064
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     926
_refine_ls_number_reflns         10827
_refine_ls_number_restraints     335
_refine_ls_restrained_S_all      1.073
_refine_ls_R_factor_all          0.0373
_refine_ls_R_factor_gt           0.0328
_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^)+(0.0194P)^2^+67.3127P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0800
_refine_ls_wR_factor_ref         0.0819
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9488
_reflns_number_total             10827
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00331d2.cif
_cod_data_source_block           2_198K
_cod_depositor_comments
'Adding full bibliography for 1571621--1571630.cif.'
_cod_original_cell_volume        12259.68(16)
_cod_database_code               1571627
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C N O Zn Au '
_chemical_oxdiff_usercomment     06-ZnAuCNO-198
_shelx_estimated_absorpt_t_max   0.601
_shelx_estimated_absorpt_t_min   0.352
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Rigid bond restraints
 C60A, C50A, H50A, C49A, C51A, H49A, C54A, C55A, C52A, H54A, C53A, C56A, H55A,
 C58A, C64A, C57A, H56A, C59A, H64A, C63A, C62A, H63A, H62A, C61A, H60A, H61A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C60A) \\sim Ueq, Uanis(C50A) \\sim Ueq, Uanis(C49A) \\sim Ueq,
Uanis(C51A) \\sim Ueq, Uanis(C54A) \\sim Ueq, Uanis(C55A) \\sim Ueq,
Uanis(C52A) \\sim Ueq, Uanis(C53A) \\sim Ueq, Uanis(C56A) \\sim Ueq,
Uanis(C58A) \\sim Ueq, Uanis(C64A) \\sim Ueq, Uanis(C57A) \\sim Ueq,
Uanis(C59A) \\sim Ueq, Uanis(C63A) \\sim Ueq, Uanis(C62A) \\sim Ueq,
Uanis(C61A) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C54) \\sim Ueq, Uanis(C49)
\\sim Ueq, Uanis(C53) \\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C64) \\sim Ueq,
Uanis(C52) \\sim Ueq, Uanis(C51) \\sim Ueq, Uanis(C63) \\sim Ueq, Uanis(C58)
\\sim Ueq, Uanis(C55) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(C57) \\sim Ueq,
Uanis(C56) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C62) \\sim Ueq, : with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(C41) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C37)
\\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C39) \\sim Ueq,
Uanis(C38) \\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C33)
\\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
4. Others
 Fixed Sof: C54(0.5) H54(0.5) C49(0.5) H49(0.5) C50(0.5) H50(0.5) C51(0.5)
 C55(0.5) H55(0.5) C56(0.5) H56(0.5) C57(0.5) C62(0.5) H62(0.5) C61(0.5)
 H61(0.5) C60(0.5) H60(0.5) C59(0.5) C63(0.5) H63(0.5) C64(0.5) H64(0.5)
 C53(0.5) C52(0.5) C58(0.5) C50A(0.5) H50A(0.5) C49A(0.5) H49A(0.5) C54A(0.5)
 H54A(0.5) C53A(0.5) C64A(0.5) H64A(0.5) C63A(0.5) H63A(0.5) C62A(0.5)
 H62A(0.5) C61A(0.5) H61A(0.5) C60A(0.5) H60A(0.5) C59A(0.5) C58A(0.5)
 C57A(0.5) C56A(0.5) H56A(0.5) C55A(0.5) H55A(0.5) C51A(0.5) C52A(0.5)
5.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C25(H25), C18(H18), C19(H19), C26(H26), C9(H9), C10(H10),
 C24(H24), C1(H1), C2(H2), C12(H12), C23(H23), C11(H11), C39(H39), C16(H16),
 C15(H15), C46(H46), C34(H34), C40(H40), C38(H38), C48(H48), C47(H47), C44(H44),
  C45(H45), C33(H33), C54(H54), C49(H49), C50(H50), C55(H55), C56(H56),
 C62(H62), C61(H61), C60(H60), C63(H63), C64(H64), C50A(H50A), C49A(H49A),
 C54A(H54A), C64A(H64A), C63A(H63A), C62A(H62A), C61A(H61A), C60A(H60A),
 C56A(H56A), C55A(H55A)
5.b Fitted hexagon refined as free rotating group:
 C62A(C61A,C60A,C59A,C58A,C57A)
;
_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
;
_oxdiff_exptl_absorpt_empirical_full_max 2.013
_oxdiff_exptl_absorpt_empirical_full_min 0.719