Single-crystal chiral two-dimensional supramolecular organic frameworks for tunable circularly polarized luminescence
Cui, Jialin; Wang, Hui; Liu, Hui; Yu, Hailong; Wang, Wei; Wang, Yu; Zhao, Yingjie; Chemical Science 16 (2025) 7513–7522; doi:10.1039/D4SC08811E

data_1574189
_publ_section_title
;
 Single-crystal chiral two-dimensional supramolecular organic frameworks
 for tunable circularly polarized luminescence
;
_journal_issue                   17
_journal_name_full               'Chemical Science'
_journal_page_first              7513
_journal_page_last               7522
_journal_paper_doi               10.1039/D4SC08811E
_journal_volume                  16
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety
'0.667(C60 H42 N6 O12), C14 H8 Cl2, C H2 Cl2, 3.52[CH2Cl2]'
_chemical_formula_sum            'C55 H38 Cl4 N4 O8'
_chemical_formula_weight         1024.69
_space_group_crystal_system      trigonal
_space_group_IT_number           155
_space_group_name_Hall           'R 3 2"'
_space_group_name_H-M_alt        'R 3 2 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-09-18
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-10-15 deposited with the CCDC.	2025-03-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            9
_cell_length_a                   24.7120(5)
_cell_length_b                   24.7120(5)
_cell_length_c                   25.1045(5)
_cell_measurement_reflns_used    7106
_cell_measurement_temperature    99.98(10)
_cell_measurement_theta_max      73.8040
_cell_measurement_theta_min      2.7000
_cell_volume                     13276.9(5)
_computing_cell_refinement       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.84a (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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.98(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 0.967
_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     53.00 103.00   0.50    1.63    --  109.82 -94.00 120.00  100
  2  \w     50.00 107.00   0.50    1.63    --  109.82-111.00 -30.00  114
  3  \w     42.00  68.00   0.50    1.63    --  109.82 -61.00-120.00   52
  4  \w     37.00  62.00   0.50    1.63    --  109.82 -61.00-150.00   50
  5  \w    -23.00  46.00   0.50    0.41    --  -36.36  19.00   0.00  138
  6  \w    -29.00   6.00   0.50    0.41    --   36.36 -59.00 -40.00   70
  7  \w     15.00  42.00   0.50    0.41    --   36.36 -59.00 -40.00   54
  8  \w     83.00 108.00   0.50    1.63    --  109.82  43.00-149.00   50
  9  \w    121.00 177.00   0.50    1.63    --  109.82  43.00-149.00  112
 10  \w     87.00 118.00   0.50    0.41    --   36.36 172.00-167.00   62
 11  \w    -47.00 -22.00   0.50    1.63    -- -102.00  45.00-180.00   50
 12  \w    -60.00 -30.00   0.50    1.63    -- -102.00  61.00-150.00   60
 13  \w    -49.00 -23.00   0.50    1.63    -- -102.00  45.00-150.00   52
 14  \w    -49.00 -23.00   0.50    1.63    -- -102.00  45.00-120.00   52
 15  \w    -49.00 -24.00   0.50    1.63    -- -102.00  45.00 -90.00   50
 16  \w    -64.00 -35.00   0.50    1.63    -- -102.00  61.00   0.00   58
 17  \w    -53.00 -27.00   0.50    1.63    -- -102.00  61.00 150.00   52
 18  \w    -49.00 -24.00   0.50    1.63    -- -102.00  45.00 120.00   50
 19  \w    -91.00 -53.00   0.50    0.41    --  -36.36-156.00 -20.00   76
 20  \w   -119.00 -55.00   0.50    1.63    -- -102.00-172.00 179.00  128
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0713572000
_diffrn_orient_matrix_UB_12      0.0438525000
_diffrn_orient_matrix_UB_13      -0.0011090000
_diffrn_orient_matrix_UB_21      -0.0028574000
_diffrn_orient_matrix_UB_22      0.0250647000
_diffrn_orient_matrix_UB_23      0.0555275000
_diffrn_orient_matrix_UB_31      0.0091080000
_diffrn_orient_matrix_UB_32      -0.0512890000
_diffrn_orient_matrix_UB_33      0.0260832000
_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  0.0262
_diffrn_reflns_av_unetI/netI     0.0323
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.967
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            15318
_diffrn_reflns_point_group_measured_fraction_full 0.967
_diffrn_reflns_point_group_measured_fraction_max 0.912
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.536
_diffrn_reflns_theta_min         2.713
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.241
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.67799
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.84a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_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    1.153
_exptl_crystal_description       cube
_exptl_crystal_F_000             4752
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.17
_refine_diff_density_max         0.498
_refine_diff_density_min         -0.428
_refine_diff_density_rms         0.097
_refine_ls_abs_structure_details
;
 Flack x determined using 1982 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.112(13)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.093
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     531
_refine_ls_number_reflns         5536
_refine_ls_number_restraints     694
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0786
_refine_ls_R_factor_gt           0.0749
_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^)+(0.1449P)^2^+28.1671P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2226
_refine_ls_wR_factor_ref         0.2266
_reflns_Friedel_coverage         0.759
_reflns_Friedel_fraction_full    0.930
_reflns_Friedel_fraction_max     0.848
_reflns_number_gt                5108
_reflns_number_total             5536
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08811e2.cif
_cod_data_source_block           dca-s
_cod_depositor_comments
'Adding full bibliography for 1574186--1574191.cif.'
_cod_original_cell_volume        13276.9(6)
_cod_original_sg_symbol_H-M      'R 3 2'
_cod_database_code               1574189
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.702
_shelx_estimated_absorpt_t_min   0.663
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C27-C28 = C29-C28 = C21-C34 = C22-C21 = C29A-C28A = C27A-C28A = C21A-C22A =
 C34A-C21A
 1.39 with sigma of 0.01
 Cl4-C35 = Cl3-C35 = Cl3A-C35A = Cl4A-C35A
 1.79 with sigma of 0.01
 Cl1-C21 = Cl2-C28
 1.74 with sigma of 0.01
 Cl2A-C28A = Cl1A-C21A
 1.74 with sigma of 0.01
 Cl3-Cl4 = Cl4A-Cl3A
 2.924 with sigma of 0.02
 Cl2-C29 \\sim Cl2-C27
 with sigma of 0.02
 Cl2A-C27A \\sim Cl2A-C29A
 with sigma of 0.02
 Cl1-C34 \\sim Cl1-C22
 with sigma of 0.02
 C27-C34 \\sim C29-C22
 with sigma of 0.02
 C29-C27 \\sim C22-C34
 with sigma of 0.02
 Cl1A-C22A \\sim Cl1A-C34A
 with sigma of 0.02
 C29A-C22A \\sim C27A-C34A
 with sigma of 0.02
 C27A-C29A \\sim C34A-C22A
 with sigma of 0.02
3. Restrained planarity
 C27, C33, C34, C32, C29, C21, C31, C28, C30, Cl1, C22, Cl2, C23, C26, C24, C25
 with sigma of 0.1
 C30A, C29A, C28A, C34A, C27A, Cl2A, C21A, C33A, C31A, C22A, C26A, Cl1A, C32A,
 C23A, C25A, C24A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Cl3A \\sim C35A \\sim Cl4A \\sim Cl3 \\sim C35 \\sim Cl4: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C33 \\sim C32 \\sim C31 \\sim C30 \\sim C29 \\sim C34 \\sim Cl2 \\sim C28 \\sim
C27 \\sim C26 \\sim C25 \\sim C24 \\sim C23 \\sim C22 \\sim C21 \\sim Cl1 \\sim
C29A \\sim C23A \\sim C24A \\sim C22A \\sim C25A \\sim C27A \\sim C21A \\sim
Cl1A \\sim C26A \\sim C28A \\sim C34A \\sim Cl2A \\sim C33A \\sim C30A \\sim
C32A \\sim C31A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
5. Others
 Sof(C29A)=Sof(C30A)=Sof(H30A)=Sof(C31A)=Sof(H31A)=Sof(C32A)=Sof(H32A)=
 Sof(C33A)=Sof(H33A)=Sof(C34A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24A)=
 Sof(C25A)=Sof(H25A)=Sof(C26A)=Sof(H26A)=Sof(C27A)=Sof(C22A)=Sof(C21A)=
 Sof(Cl1A)=Sof(C28A)=Sof(Cl2A)=0.5*(1-FVAR(2))
 Sof(C33)=Sof(H33)=Sof(C32)=Sof(H32)=Sof(C31)=Sof(H31)=Sof(C30)=Sof(H30)=
 Sof(C29)=Sof(C34)=Sof(Cl2)=Sof(C28)=Sof(C27)=Sof(C26)=Sof(H26)=Sof(C25)=
 Sof(H25)=Sof(C24)=Sof(H24)=Sof(C23)=Sof(H23)=Sof(C22)=Sof(C21)=Sof(Cl1)=0.5*
 FVAR(2)
 Sof(C35A)=Sof(H35C)=Sof(H35D)=Sof(Cl3A)=Sof(Cl4A)=0.5*(1-FVAR(3))
 Sof(Cl3)=Sof(C35)=Sof(H35A)=Sof(H35B)=Sof(Cl4)=0.5*FVAR(3)
6.a Ternary CH refined with riding coordinates:
 C1(H1), C2(H2)
6.b Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B), C3(H3A,H3B), C5(H5A,H5B), C4(H4A,H4B), C35(H35A,H35B), C35A(H35C,
 H35D)
6.c Aromatic/amide H refined with riding coordinates:
 C33(H33), C32(H32), C31(H31), C30(H30), C16(H16), C9(H9), C15(H15), C10(H10),
 C26(H26), C25(H25), C24(H24), C23(H23), C30A(H30A), C31A(H31A), C32A(H32A),
 C33A(H33A), C23A(H23A), C24A(H24A), C25A(H25A), C26A(H26A)
6.d Fitted hexagon refined as free rotating group:
 C33(C32,C31,C30,C29,C34), C27(C26,C25,C24,C23,C22), C29A(C30A,C31A,C32A,C33A,
 C34A), C23A(C24A,C25A,C26A,C27A,C22A)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 1335 electrons were 
found in a volume of 3920\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
3.52[CH2Cl2] per Asymmetric Unit 
which account for 1331 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              49686
_shelx_fab_checksum              3160
_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 1.404
_oxdiff_exptl_absorpt_empirical_full_min 0.562