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_1574188
_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
'2(C60 H42 N6 O12), 3(C20 H12), C6 H14, 7(C H Cl3)'
_chemical_formula_sum            'C193 H141 Cl21 N12 O24'
_chemical_formula_weight         3756.62
_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             2024-09-17
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-10-17 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            3
_cell_length_a                   24.0509(4)
_cell_length_b                   24.0509(4)
_cell_length_c                   25.9832(4)
_cell_measurement_reflns_used    24334
_cell_measurement_temperature    99.98(10)
_cell_measurement_theta_max      74.3910
_cell_measurement_theta_min      2.7000
_cell_volume                     13016.3(4)
_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 1.000
_diffrn_measured_fraction_theta_max 0.986
_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    -71.00 -45.00   0.50    0.35    --  -41.52  -9.00  34.00   52
  2  \w    -17.00   8.00   0.50    0.35    --  -41.52   9.00-151.00   50
  3  \w     12.00  63.00   0.50    0.35    --   41.52   9.00-151.00  102
  4  \w    -30.00  -5.00   0.50    0.35    --   41.52  -9.00  34.00   50
  5  \w   -125.00-100.00   0.50    1.38    -- -102.00  -9.00  34.00   50
  6  \w     62.00 147.00   0.50    1.38    --  107.17   9.00-151.00  170
  7  \w    -40.00  35.00   0.50    0.35    --  -41.52  37.00-120.00  150
  8  \w     20.00  75.00   0.50    0.35    --   41.52  57.00-120.00  110
  9  \w     14.00 114.00   0.50    0.35    --   41.52  77.00 -90.00  200
 10  \w     90.00 115.00   0.50    0.35    --   41.52  77.00   0.00   50
 11  \w     18.00  44.00   0.50    0.35    --   41.52  77.00 120.00   52
 12  \w     13.00  82.00   0.50    0.35    --   41.52  77.00   0.00  138
 13  \w     82.00 112.00   0.50    0.35    --   41.52  77.00 -60.00   60
 14  \w     22.00  91.00   0.50    0.35    --   41.52-125.00 -90.00  138
 15  \w     81.00 112.00   0.50    0.35    --   41.52  57.00-120.00   62
 16  \w     19.00  44.00   0.50    0.35    --   41.52  77.00 150.00   50
 17  \w     20.00  74.00   0.50    0.35    --   41.52  77.00 -60.00  108
 18  \w     21.00  59.00   0.50    0.35    --   41.52  37.00-120.00   76
 19  \w    -99.00 -73.00   0.50    1.38    -- -102.00 -77.00 -60.00   52
 20  \w   -175.00-121.00   0.50    1.38    -- -102.00 -77.00 -60.00  108
 21  \w   -175.00 -78.00   0.50    1.38    -- -102.00 -61.00  30.00  194
 22  \w   -101.00 -75.00   0.50    1.38    -- -102.00 -71.00 -81.89   52
 23  \w   -104.00 -78.00   0.50    1.38    -- -102.00 -61.00 -90.00   52
 24  \w    -99.00 -74.00   0.50    1.38    -- -102.00 -74.00 -39.56   50
 25  \w   -104.00 -78.00   0.50    1.38    -- -102.00 -61.00   0.00   52
 26  \w   -172.00-147.00   0.50    1.38    -- -102.00 -74.00 -39.56   50
 27  \w   -108.00 -74.00   0.50    1.38    -- -102.00 -77.00-120.00   68
 28  \w   -102.00 -77.00   0.50    1.38    -- -102.00 -67.00  -4.21   50
 29  \w   -159.00-133.00   0.50    1.38    -- -102.00 -61.00  11.74   52
 30  \w   -175.00-147.00   0.50    1.38    -- -102.00 -71.00 -81.89   56
 31  \w   -103.00 -77.00   0.50    1.38    -- -102.00 -77.00 -90.00   52
 32  \w   -170.00-114.00   0.50    1.38    -- -102.00 -45.00-120.00  112
 33  \w   -106.00 -81.00   0.50    1.38    -- -102.00 -39.00-105.69   50
 34  \w   -174.00-148.00   0.50    1.38    -- -102.00 -77.00 -44.55   52
 35  \w    -98.00 -73.00   0.50    1.38    -- -102.00 -77.00 -44.55   50
 36  \w   -102.00 -77.00   0.50    1.38    -- -102.00 -73.00  37.68   50
 37  \w   -124.00 -77.00   0.50    1.38    -- -102.00 -67.00  11.19   94
 38  \w    -99.00 -74.00   0.50    1.38    -- -102.00 -74.00 -17.39   50
 39  \w   -175.00-142.00   0.50    1.38    -- -102.00 -67.00  -4.21   66
 40  \w   -103.00 -78.00   0.50    1.38    -- -102.00 -61.00   3.47   50
 41  \w   -173.00 -80.00   0.50    1.38    -- -102.00 -45.00 -30.00  186
 42  \w   -160.00-135.00   0.50    1.38    -- -102.00 -74.00 -17.39   50
 43  \w    -99.00 -74.00   0.50    1.38    -- -102.00 -77.00  30.00   50
 44  \w    -99.00 -74.00   0.50    1.38    -- -102.00 -75.00 -45.46   50
 45  \w   -114.00 -82.00   0.50    1.38    -- -102.00 -45.00 -90.00   64
 46  \w   -174.00-117.00   0.50    1.38    -- -102.00 -66.00 -68.20  114
 47  \w   -102.00 -77.00   0.50    1.38    -- -102.00 -66.00 -68.20   50
 48  \w    -70.00 -45.00   0.50    1.38    -- -102.00  77.00 -30.00   50
 49  \w   -173.00 -78.00   0.50    1.38    -- -102.00 -65.00-123.16  190
 50  \w   -103.00 -78.00   0.50    1.38    -- -102.00 -61.00-120.00   50
 51  \w   -104.00 -71.00   0.50    1.38    -- -102.00  77.00 -30.00   66
 52  \w   -155.00 -82.00   0.50    1.38    -- -102.00 -57.00 -47.82  146
 53  \w   -102.00 -77.00   0.50    1.38    -- -102.00 -68.00  -8.20   50
 54  \w   -103.00 -78.00   0.50    1.38    -- -102.00 -65.00 -55.40   50
 55  \w   -103.00 -78.00   0.50    1.38    -- -102.00 -61.00  11.74   50
 56  \w   -102.00 -77.00   0.50    1.38    -- -102.00 -66.00   4.34   50
 57  \w   -102.00 -77.00   0.50    1.38    -- -102.00 -70.00 -31.53   50
 58  \w   -100.00 -75.00   0.50    1.38    -- -102.00 -77.00 -30.00   50
 59  \w   -100.00 -75.00   0.50    1.38    -- -102.00 -72.00 -91.57   50
 60  \w   -108.00 -83.00   0.50    1.38    -- -102.00 -45.00-120.00   50
 61  \w    -99.00 -74.00   0.50    1.38    -- -102.00 -77.00   0.00   50
 62  \w   -105.00 -80.00   0.50    1.38    -- -102.00 -41.00 -84.49   50
 63  \w   -105.00 -80.00   0.50    1.38    -- -102.00 -42.00 -19.82   50
 64  \w   -107.00 -82.00   0.50    1.38    -- -102.00 -43.00  -4.89   50
 65  \w   -104.00 -79.00   0.50    1.38    -- -102.00 -44.00 -48.88   50
 66  \w   -104.00 -79.00   0.50    1.38    -- -102.00 -57.00 -45.50   50
 67  \w   -103.00 -78.00   0.50    1.38    -- -102.00 -61.00 -30.00   50
 68  \w     36.00 112.00   0.50    1.38    --  107.17-125.00  30.00  152
 69  \w     35.00  72.00   0.50    1.38    --  107.17 -61.00-150.00   74
 70  \w     38.00  78.00   0.50    1.38    --  107.17 -94.00 150.00   80
 71  \w     79.00 105.00   0.50    1.38    --  107.17 -94.00-120.00   52
 72  \w     75.00 104.00   0.50    1.38    --  107.17 -94.00-150.00   58
 73  \w     36.00  98.00   0.50    1.38    --  107.17 -94.00 -60.00  124
 74  \w     34.00  71.00   0.50    1.38    --  107.17 -94.00-120.00   74
 75  \w    153.00 178.00   0.50    1.38    --  107.17  77.00 -30.00   50
 76  \w     46.00  72.00   0.50    1.38    --  107.17 -94.00-150.00   52
 77  \w     78.00 104.00   0.50    1.38    --  107.17  77.00 -30.00   52
;
_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      0.0229571667
_diffrn_orient_matrix_UB_12      0.0543777333
_diffrn_orient_matrix_UB_13      0.0401019333
_diffrn_orient_matrix_UB_21      0.0315486333
_diffrn_orient_matrix_UB_22      0.0501536667
_diffrn_orient_matrix_UB_23      -0.0430928333
_diffrn_orient_matrix_UB_31      -0.0628471333
_diffrn_orient_matrix_UB_32      0.0014523333
_diffrn_orient_matrix_UB_33      -0.0070262667
_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  0.0655
_diffrn_reflns_av_unetI/netI     0.0258
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       29
_diffrn_reflns_limit_k_min       -29
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            74883
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.839
_diffrn_reflns_theta_min         2.719
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.638
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68857
_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 greenish green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   greenish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.438
_exptl_crystal_description       cube
_exptl_crystal_F_000             5796
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.05
_refine_diff_density_max         0.740
_refine_diff_density_min         -0.390
_refine_diff_density_rms         0.061
_refine_ls_abs_structure_details
;
 Flack x determined using 2198 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.041(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     565
_refine_ls_number_reflns         5908
_refine_ls_number_restraints     370
_refine_ls_restrained_S_all      1.098
_refine_ls_R_factor_all          0.0721
_refine_ls_R_factor_gt           0.0681
_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^)+(0.1092P)^2^+23.9187P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1871
_refine_ls_wR_factor_ref         0.1907
_reflns_Friedel_coverage         0.843
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.963
_reflns_number_gt                5510
_reflns_number_total             5908
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08811e2.cif
_cod_data_source_block           bei-r
_cod_depositor_comments
'Adding full bibliography for 1574186--1574191.cif.'
_cod_original_cell_volume        13016.2(5)
_cod_original_sg_symbol_H-M      'R 3 2'
_cod_database_code               1574188
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.839
_shelx_estimated_absorpt_t_min   0.785
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl4-C38 = Cl6-C38 = Cl5-C38
 1.79 with sigma of 0.01
 C33-C32 = C34-C33 = C35-C34 = C36-C35 = C37-C36
 1.54 with sigma of 0.01
 Cl4-Cl5 = Cl4-Cl6 = Cl5-Cl6
 2.924 with sigma of 0.02
 C34-C32 = C33-C35 = C35-C37 = C36-C34
 2.515 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C34 \\sim C32 \\sim C33 \\sim C35 \\sim C36 \\sim C37: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C31 \\sim Cl1 \\sim Cl2 \\sim Cl3 \\sim C31A \\sim Cl1A \\sim Cl2A \\sim Cl3A
\\sim C31B \\sim Cl2B \\sim Cl3B \\sim Cl1B: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
Cl4 \\sim C38 \\sim Cl5 \\sim Cl6 \\sim C38A \\sim Cl4A \\sim Cl6A \\sim Cl5A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(Cl4) \\sim Ueq, Uanis(C38) \\sim Ueq, Uanis(Cl5) \\sim Ueq, Uanis(Cl6)
\\sim Ueq, Uanis(C38A) \\sim Ueq, Uanis(Cl4A) \\sim Ueq, Uanis(Cl6A) \\sim Ueq,
Uanis(Cl5A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C32) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C34) \\sim Ueq, Uanis(C35)
\\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C37) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C31B) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
4. Same fragment restrains
{C31A, Cl1A, Cl2A, Cl3A} sigma for 1-2: 0.02, 1-3: 0.02
{C31B, Cl1B, Cl2B, Cl3B} sigma for 1-2: 0.02, 1-3: 0.02
as in
{C31, Cl1, Cl2, Cl3}
{C38A, Cl4A, Cl5A, Cl6A} sigma for 1-2: 0.02, 1-3: 0.02
as in
{C38, Cl4, Cl6, Cl5}
5. Others
 1*[Sof(C31)+Sof(H31)+Sof(Cl1)+Sof(Cl2)+Sof(Cl3)]+1*[Sof(C31A)+Sof(H31A)+
 Sof(Cl1A)+Sof(Cl2A)+Sof(Cl3A)]+1*[Sof(C31B)+Sof(H31B)+Sof(Cl1B)+Sof(Cl2B)+
 Sof(Cl3B)]=1 with esd of 0.0001
 Sof(C31)=Sof(H31)=Sof(Cl1)=Sof(Cl2)=Sof(Cl3)=FVAR(1)
 Sof(C31A)=Sof(H31A)=Sof(Cl1A)=Sof(Cl2A)=Sof(Cl3A)=FVAR(2)
 Sof(C31B)=Sof(H31B)=Sof(Cl1B)=Sof(Cl2B)=Sof(Cl3B)=FVAR(3)
 Sof(C38A)=Sof(H38A)=Sof(Cl4A)=Sof(Cl5A)=Sof(Cl6A)=0.16667*(1-FVAR(5))
 Sof(C38)=Sof(H38)=Sof(Cl4)=Sof(Cl6)=Sof(Cl5)=0.16667*FVAR(5)
 Fixed Sof: C32(0.16667) H32A(0.16667) H32B(0.16667) H32C(0.16667)
 C33(0.16667) H33A(0.16667) H33B(0.16667) C34(0.16667) H34A(0.16667)
 H34B(0.16667) C35(0.16667) H35A(0.16667) H35B(0.16667) C36(0.16667)
 H36A(0.16667) H36B(0.16667) C37(0.16667) H37A(0.16667) H37B(0.16667)
 H37C(0.16667)
6.a Ternary CH refined with riding coordinates:
 C31(H31), C1(H1), C2(H2), C31A(H31A), C31B(H31B), C38(H38), C38A(H38A)
6.b Secondary CH2 refined with riding coordinates:
 C3(H3A,H3B), C5(H5A,H5B), C6(H6A,H6B), C4(H4A,H4B), C33(H33A,H33B), C34(H34A,
 H34B), C35(H35A,H35B), C36(H36A,H36B)
6.c Aromatic/amide H refined with riding coordinates:
 C9(H9), C16(H16), C15(H15), C22(H22), C10(H10), C23(H23), C24(H24), C29(H29),
 C30(H30), C28(H28)
6.d Idealised Me refined as rotating group:
 C32(H32A,H32B,H32C), C37(H37A,H37B,H37C)
;
_shelx_res_checksum              45293