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_1571629
_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             2024-04-29
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-04-30 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                   15.40483(13)
_cell_length_b                   27.6851(2)
_cell_length_c                   28.6645(2)
_cell_measurement_reflns_used    74300
_cell_measurement_temperature    145.00(10)
_cell_measurement_theta_max      77.0210
_cell_measurement_theta_min      3.1060
_cell_volume                     12224.96(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      145.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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     37.00 109.00   0.50    0.15    --  123.00-112.00 120.00  144
  2  \w     72.00 107.00   0.50    0.15    --   69.84-125.00  30.00   70
  3  \w     37.00  62.00   0.50    0.15    --   69.84-125.00  30.00   50
  4  \w     75.00 109.00   0.50    0.15    --  123.00-112.00  30.00   68
  5  \w     83.00 109.00   0.50    0.15    --  123.00-112.00  90.00   52
  6  \w     53.00  78.00   0.50    0.15    --  123.00-112.00 -60.00   50
  7  \w     84.00 109.00   0.50    0.15    --  123.00-112.00 -60.00   50
  8  \w     84.00 109.00   0.50    0.15    --  123.00-112.00-120.00   50
  9  \w     37.00 109.00   0.50    0.15    --  123.00-112.00-180.00  144
 10  \w     39.00  65.00   0.50    0.15    --  123.00-112.00-150.00   52
 11  \w     38.00  75.00   0.50    0.15    --  123.00-112.00-120.00   74
 12  \w     78.00 107.00   0.50    0.15    --  123.00-112.00-150.00   58
 13  \w     49.00  98.00   0.50    0.15    --  123.00 -92.00-150.00   98
 14  \w     31.00  99.00   0.50    0.15    --  123.00 -92.00-120.00  136
 15  \w     83.00 109.00   0.50    0.15    --  123.00-112.00 -30.00   52
 16  \w     45.00  71.00   0.50    0.15    --  123.00-112.00  30.00   52
 17  \w     43.00  88.00   0.50    0.15    --  123.00 -92.00 150.00   90
 18  \w     39.00  91.00   0.50    0.15    --  123.00 -92.00 120.00  104
 19  \w    -21.00  19.00   0.50    0.15    --   69.84 -15.00  30.00   80
 20  \w     60.00  96.00   0.50    0.15    --  123.00 -77.00 -90.00   72
 21  \w     33.00  77.00   0.50    0.15    --  123.00 -77.00 -30.00   88
 22  \w     41.00  66.00   0.50    0.15    --  123.00 -64.00   0.00   50
 23  \w     49.00  94.00   0.50    0.15    --  123.00 -77.00   0.00   90
 24  \w     41.00  73.00   0.50    0.15    --  123.00 -64.00 -60.00   64
 25  \w     40.00  73.00   0.50    0.15    --  123.00 -64.00 -90.00   66
 26  \w    -13.00  48.00   0.50    0.15    --   69.84 -45.00 -90.00  122
 27  \w    -16.00  47.00   0.50    0.15    --   69.84 -45.00-180.00  126
 28  \w     37.00 101.00   0.50    0.15    --  123.00 -77.00  30.00  128
 29  \w     40.00  65.00   0.50    0.15    --  123.00 -64.00  60.00   50
 30  \w     43.00  69.00   0.50    0.15    --  123.00 -64.00 150.00   52
 31  \w    -25.00   0.00   0.50    0.15    --   69.84 -15.00 150.00   50
 32  \w     34.00 175.00   0.50    0.15    --  123.00  12.00  60.00  282
 33  \w    125.00 169.00   0.50    0.15    --  123.00  77.00 120.00   88
 34  \w    103.00 139.00   0.50    0.15    --  123.00  77.00  30.00   72
 35  \w    150.00 175.00   0.50    0.15    --  123.00  77.00  30.00   50
 36  \w     77.00 109.00   0.50    0.15    --  123.00  77.00 120.00   64
 37  \w     88.00 116.00   0.50    0.15    --  123.00  64.00  60.00   56
 38  \w    133.00 174.00   0.50    0.15    --  123.00  64.00  60.00   82
 39  \w     89.00 153.00   0.50    0.15    --  123.00  50.00 -90.00  128
 40  \w     65.00 171.00   0.50    0.15    --  123.00  38.00-150.00  212
 41  \w     28.00 169.00   0.50    0.15    --  123.00  12.00-180.00  282
 42  \w    -23.00  99.00   0.50    0.06    --   16.67  77.00   0.00  244
 43  \w     25.00  94.00   0.50    0.15    --   69.84  77.00-180.00  138
 44  \w    103.00 129.00   0.50    0.15    --   69.84  77.00-180.00   52
 45  \w     74.00 121.00   0.50    0.15    --  123.00 179.00 -30.00   94
 46  \w     93.00 132.00   0.50    0.15    --  123.00 179.00  30.00   78
 47  \w     65.00  91.00   0.50    0.15    --  123.00 179.00  30.00   52
 48  \w     61.00  99.00   0.50    0.15    --  123.00 179.00 120.00   76
 49  \w    120.00 146.00   0.50    0.15    --  123.00 179.00 120.00   52
 50  \w     45.00  72.00   0.50    0.06    --   16.67 179.00  30.00   54
 51  \w     50.00  99.00   0.50    0.06    --   16.67 179.00 -60.00   98
 52  \w     51.00  78.00   0.50    0.06    --   16.67 179.00-120.00   54
 53  \w    -41.00  -4.00   0.50    0.15    --  -69.84  45.00-180.00   74
 54  \w    -85.00 -60.00   0.50    0.15    --  -69.84  77.00-180.00   50
 55  \w    -71.00  13.00   0.50    0.15    --  -69.84  61.00  30.00  168
 56  \w     -3.00  65.00   0.50    0.06    --  -16.67  57.00  90.00  136
 57  \w    -56.00 -31.00   0.50    0.06    --  -16.67  57.00  90.00   50
 58  \w    -54.00  13.00   0.50    0.15    --  -69.84  45.00  90.00  134
 59  \w    -46.00 -14.00   0.50    0.15    --  -97.00  38.00 150.00   64
 60  \w    -46.00 -19.00   0.50    0.15    --  -97.00  38.00 120.00   54
 61  \w    -41.00 -14.00   0.50    0.15    --  -97.00  38.00  60.00   54
 62  \w    -41.00 -14.00   0.50    0.15    --  -97.00  38.00  30.00   54
 63  \w    -22.00  11.00   0.50    0.15    --  -69.84  15.00  30.00   66
 64  \w    -27.00  13.00   0.50    0.15    --  -69.84  15.00 -30.00   80
 65  \w    -45.00 -20.00   0.50    0.15    --  -97.00  38.00 -60.00   50
 66  \w    -27.00  12.00   0.50    0.15    --  -69.84  15.00-180.00   78
 67  \w    -45.00 -20.00   0.50    0.15    --  -97.00  38.00-150.00   50
 68  \w   -151.00-125.00   0.50    0.15    --  -69.84-125.00 120.00   52
 69  \w   -111.00 -85.00   0.50    0.15    --  -69.84-125.00 120.00   52
 70  \w   -112.00 -86.00   0.50    0.15    --  -69.84-125.00 -30.00   52
 71  \w   -152.00-126.00   0.50    0.15    --  -69.84-125.00 -30.00   52
 72  \w   -109.00 -28.00   0.50    0.15    --  -69.84 125.00-180.00  162
 73  \w   -148.00-122.00   0.50    0.15    --  -97.00 179.00-150.00   52
 74  \w   -111.00 -69.00   0.50    0.15    --  -97.00 179.00-150.00   84
;
_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      0.0638234000
_diffrn_orient_matrix_UB_12      0.0423975000
_diffrn_orient_matrix_UB_13      0.0062191000
_diffrn_orient_matrix_UB_21      -0.0714110000
_diffrn_orient_matrix_UB_22      0.0293872000
_diffrn_orient_matrix_UB_23      0.0246186000
_diffrn_orient_matrix_UB_31      0.0288258000
_diffrn_orient_matrix_UB_32      -0.0208679000
_diffrn_orient_matrix_UB_33      0.0473575000
_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  0.0842
_diffrn_reflns_av_unetI/netI     0.0304
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       32
_diffrn_reflns_limit_k_min       -32
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            125252
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        66.600
_diffrn_reflns_theta_max         66.600
_diffrn_reflns_theta_min         3.083
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    18.934
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45492
_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    2.151
_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         2.278
_refine_diff_density_min         -3.172
_refine_diff_density_rms         0.168
_refine_ls_extinction_coef       0.0000026(8)
_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   1.116
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     926
_refine_ls_number_reflns         10796
_refine_ls_number_restraints     335
_refine_ls_restrained_S_all      1.108
_refine_ls_R_factor_all          0.0513
_refine_ls_R_factor_gt           0.0458
_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^)+(0.0462P)^2^+170.1670P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1359
_refine_ls_wR_factor_ref         0.1388
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9408
_reflns_number_total             10796
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc00331d2.cif
_cod_data_source_block           2_145K
_cod_depositor_comments
'Adding full bibliography for 1571621--1571630.cif.'
_cod_original_cell_volume        12224.95(17)
_cod_database_code               1571629
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         ZnAuCNO
_chemical_oxdiff_usercomment     06-ZnAuCNO-145
_shelx_estimated_absorpt_t_max   0.600
_shelx_estimated_absorpt_t_min   0.351
_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
Uanis(C51A) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C54A)
\\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(C59) \\sim Ueq: with sigma of 0.005 and
sigma for terminal atoms of 0.01
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 1.886
_oxdiff_exptl_absorpt_empirical_full_min 0.735