Photosalient effect and reversible photochromic photoluminescence driven by cascade [2 + 2] cycloaddition reaction and water adsorption in a 0D hybrid metal halide.
Chen, Chudong; Li, Ziquan; Xiao, Yonghong; Ye, Chenghao; Wei, Jianwu; Zeng, Ruosheng; Pang, Qi; Luo, Binbin; Chemical science 16 (2025) 13731–13740; doi:10.1039/d5sc03344f

data_1574920
_publ_section_title
;
 Photosalient effect and reversible photochromic photoluminescence driven
 by cascade [2 + 2] cycloaddition reaction and water adsorption in a 0D
 hybrid metal halide.
;
_journal_issue                   30
_journal_name_full               'Chemical science'
_journal_page_first              13731
_journal_page_last               13740
_journal_paper_doi               10.1039/d5sc03344f
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'Cl5 H2 In O, 2(C13 H12 N)'
_chemical_formula_sum            'C26 H26 Cl5 In N2 O'
_chemical_formula_weight         674.56
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-08-01
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.17 svn.r577a77a9 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2025-03-26 deposited with the CCDC.	2025-06-23 downloaded from the CCDC.
;
_cell_angle_alpha                99.720(4)
_cell_angle_beta                 92.935(3)
_cell_angle_gamma                98.493(3)
_cell_formula_units_Z            2
_cell_length_a                   10.8192(4)
_cell_length_b                   11.7903(5)
_cell_length_c                   11.9138(5)
_cell_measurement_reflns_used    6759
_cell_measurement_temperature    199.99(10)
_cell_measurement_theta_max      69.7950
_cell_measurement_theta_min      4.1050
_cell_volume                     1476.98(11)
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      199.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.960
_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    -23.00   3.00   0.50    0.50    --    0.00  57.00 150.00   52
  2  \w    -88.00 -41.00   0.50    0.50    --    0.00 -57.00-150.00   94
  3  \w    -12.00  25.00   0.50    0.50    --    0.00 -57.00-150.00   74
  4  \w     28.00  86.00   0.50    0.50    --    0.00  38.00-150.00  116
  5  \w     31.00  80.00   0.50    0.50    --    0.00  57.00 150.00   98
  6  \w    -28.00   4.00   0.50    0.50    --    0.00  38.00-150.00   64
  7  \w     76.00 112.00   0.50    1.35    --   87.20 -61.00   0.00   72
  8  \w     -2.00  73.00   0.50    1.35    --   87.20 -61.00   0.00  150
  9  \w      0.00 116.00   0.50    1.35    --   87.20 -61.00 150.00  232
 10  \w     84.00 109.00   0.50    1.35    --   87.20 -82.00  60.00   50
 11  \w     79.00 176.00   0.50    1.35    --   87.20  45.00-150.00  194
 12  \w     59.00  85.00   0.50    1.35    --   87.20  77.00 -60.00   52
 13  \w     95.00 150.00   0.50    1.35    --   87.20  77.00 -60.00  110
 14  \w     74.00 177.00   0.50    1.35    --   87.20  45.00-120.00  206
 15  \w     -2.00 121.00   0.50    1.35    --   87.20 -82.00 150.00  246
 16  \w     15.00 124.00   0.50    1.35    --   87.20 -82.00 -60.00  218
 17  \w     99.00 124.00   0.50    1.35    --   87.20 -82.00-180.00   50
 18  \w     82.00 109.00   0.50    1.35    --   87.20 -30.00   0.00   54
 19  \w     16.00  42.00   0.50    1.35    --   87.20 -82.00   0.00   52
 20  \w     88.00 124.00   0.50    1.35    --   87.20 -82.00   0.00   72
 21  \w     57.00 101.00   0.50    1.35    --   87.20 -61.00 -60.00   88
 22  \w     -2.00  35.00   0.50    1.35    --   87.20 -61.00 -60.00   74
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0626157000
_diffrn_orient_matrix_UB_12      0.0452104000
_diffrn_orient_matrix_UB_13      0.1083530000
_diffrn_orient_matrix_UB_21      0.1269322000
_diffrn_orient_matrix_UB_22      0.0703021000
_diffrn_orient_matrix_UB_23      0.0533341000
_diffrn_orient_matrix_UB_31      -0.0286746000
_diffrn_orient_matrix_UB_32      0.1050827000
_diffrn_orient_matrix_UB_33      -0.0522710000
_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  0.0260
_diffrn_reflns_av_unetI/netI     0.0308
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.960
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            13927
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.960
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.059
_diffrn_reflns_theta_min         3.776
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    10.725
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.52478
_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 colourless'
_exptl_crystal_density_diffrn    1.517
_exptl_crystal_description       block
_exptl_crystal_F_000             676
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.822
_refine_diff_density_min         -1.377
_refine_diff_density_rms         0.127
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     449
_refine_ls_number_reflns         5387
_refine_ls_number_restraints     656
_refine_ls_restrained_S_all      0.988
_refine_ls_R_factor_all          0.0894
_refine_ls_R_factor_gt           0.0801
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1353P)^2^+6.4282P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2314
_refine_ls_wR_factor_ref         0.2420
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4560
_reflns_number_total             5387
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03344f11.cif
_cod_data_source_block           1a
_cod_depositor_comments
'Adding full bibliography for 1574919--1574921.cif.'
_cod_original_cell_volume        1476.97(11)
_cod_database_code               1574920
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         InClCNH
_chemical_oxdiff_usercomment     Stpy-InCl3-450
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All O(H,H) groups
2. Restrained distances
 C21-C22B = C20-C17A
 1.5 with sigma of 0.02
 C4A-C3A \\sim C4B-C3B
 with sigma of 0.02
 C4A-C5A \\sim C4B-C5B
 with sigma of 0.02
 C4A-C7A \\sim C4B-C7A
 with sigma of 0.02
 C3A-C2A \\sim C3B-C2B
 with sigma of 0.02
 C4A-C2A \\sim C4B-C2B
 with sigma of 0.04
 C5A-C6A \\sim C5B-C6B
 with sigma of 0.02
 C4A-C6A \\sim C4B-C6B
 with sigma of 0.04
 C2A-C1A \\sim C2B-C1B
 with sigma of 0.02
 C4A-C7B \\sim C4B-C7B
 with sigma of 0.04
 C1A-C6A \\sim C1B-C6B
 with sigma of 0.02
 C3A-C5A \\sim C3B-C5B
 with sigma of 0.04
 C3A-C7A \\sim C3B-C7A
 with sigma of 0.04
 C3A-C1A \\sim C3B-C1B
 with sigma of 0.04
 C3A-C7B \\sim C3B-C7B
 with sigma of 0.04
 C5A-C7A \\sim C5B-C7A
 with sigma of 0.04
 C5A-C1A \\sim C5B-C1B
 with sigma of 0.04
 C5A-C7B \\sim C5B-C7B
 with sigma of 0.04
 C2A-C6A \\sim C2B-C6B
 with sigma of 0.04
 C6A-C7B \\sim C6B-C7B
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C1A \\sim C1B \\sim C2A \\sim C2B \\sim C3A \\sim C3B \\sim C4A \\sim C4B \\sim
C5A \\sim C5B \\sim C6A \\sim C6B \\sim C7A \\sim C7B \\sim C8A \\sim C8B:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
N2A \\sim N2B \\sim C14A \\sim C14B \\sim C15A \\sim C15B \\sim C16A \\sim C16B
\\sim C17A \\sim C17B \\sim C18A \\sim C18B \\sim C19A \\sim C19B \\sim C20
\\sim C21 \\sim C22A \\sim C22B \\sim C23A \\sim C23B \\sim C24A \\sim C24B
\\sim C25A \\sim C25B \\sim C26A \\sim C26B: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
4. Others
 Sof(C1B)=Sof(H1B)=Sof(C2B)=Sof(H2BA)=Sof(C3B)=Sof(H3B)=Sof(C4B)=Sof(C5B)=
 Sof(H5B)=Sof(C6B)=Sof(H6B)=Sof(C7B)=Sof(H7B)=Sof(C8B)=Sof(H8B)=1-FVAR(1)
 Sof(C1A)=Sof(H1A)=Sof(C2A)=Sof(H2AA)=Sof(C3A)=Sof(H3A)=Sof(C4A)=Sof(C5A)=
 Sof(H5A)=Sof(C6A)=Sof(H6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(H8A)=FVAR(1)
 Sof(C15B)=Sof(H15B)=Sof(C16B)=Sof(H16B)=Sof(C17B)=Sof(H17B)=Sof(C18B)=
 Sof(C19B)=Sof(H19B)=Sof(C14B)=Sof(H14B)=Sof(H20A)=Sof(H21A)=Sof(C23B)=
 Sof(H23B)=Sof(C24B)=Sof(H24B)=Sof(N2B)=Sof(H2B)=Sof(C25B)=Sof(H25B)=Sof(C26B)=
 Sof(H26B)=Sof(C22B)=1-FVAR(2)
 Sof(C16A)=Sof(H16A)=Sof(C15A)=Sof(H15A)=Sof(C14A)=Sof(H14A)=Sof(C19A)=
 Sof(H19A)=Sof(C18A)=Sof(H18A)=Sof(C17A)=Sof(H20)=Sof(H21)=Sof(C25A)=Sof(H25A)=
 Sof(C26A)=Sof(H26A)=Sof(C22A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24A)=Sof(N2A)=
 Sof(H2A)=FVAR(2)
 Fixed X: C4B(-0.062411)
5.a Ternary CH refined with riding coordinates:
 C7A(H7A), C7B(H7B), C8A(H8A), C8B(H8B), C20(H20), C20(H20A), C21(H21),
 C21(H21A)
5.b Aromatic/amide H refined with riding coordinates:
 N1(H1), C1A(H1A), C1B(H1B), C2A(H2AA), C2B(H2BA), C3A(H3A), C3B(H3B),
 C5A(H5A), C5B(H5B), C6A(H6A), C6B(H6B), C10(H10), C11(H11), C12(H12), C13(H13),
  C15B(H15B), C16B(H16B), C17B(H17B), C19B(H19B), C14B(H14B), C16A(H16A),
 C15A(H15A), C14A(H14A), C19A(H19A), C18A(H18A), C23B(H23B), C24B(H24B),
 N2B(H2B), C25B(H25B), C26B(H26B), C25A(H25A), C26A(H26A), C23A(H23A),
 C24A(H24A), N2A(H2A)
5.c Fitted hexagon refined as free rotating group:
 C15B(C16B,C17B,C18B,C19B,C14B), C16A(C15A,C14A,C19A,C18A,C17A), C23B(C24B,N2B,
 C25B,C26B,C22B), C25A(C26A,C22A,C23A,C24A,N2A)
5.d X=CH2 refined with riding coordinates:
 O1(H1C,H1D)
;
_shelx_res_checksum              34210
_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 1.562
_oxdiff_exptl_absorpt_empirical_full_min 0.722