Highly enhanced chiroptical effect from self-inclusion helical nanocrystals of tetraphenylethylene bimacrocycles.
Hu, Ming; Ye, Feng-Ying; Yu, Wei; Sheng, Kang; Xu, Zhi-Rong; Fu, Jin-Jin; Wen, Xin; Feng, Hai-Tao; Liu, Minghua; Zheng, Yan-Song; Chemical science 15 (2024) 16627–16636; doi:10.1039/d4sc03599b

data_1572552
_publ_section_title
;
 Highly enhanced chiroptical effect from self-inclusion helical
 nanocrystals of tetraphenylethylene bimacrocycles.
;
_journal_issue                   40
_journal_name_full               'Chemical science'
_journal_page_first              16627
_journal_page_last               16636
_journal_paper_doi               10.1039/d4sc03599b
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         '4(Cl), C98 H108 N8 O8, 2(C4 H8 O2), 0.111[]'
_chemical_formula_sum            'C106 H124 Cl4 N8 O12'
_chemical_formula_weight         1843.92
_space_group_crystal_system      trigonal
_space_group_IT_number           146
_space_group_name_Hall           'R 3'
_space_group_name_H-M_alt        'R 3 :H'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2023-09-18
_audit_creation_method
;
Olex2 1.5
(compiled 2023.08.24 svn.re1ec1418 for OlexSys, GUI svn.r6817)
;
_audit_update_record
;
2024-06-01 deposited with the CCDC.	2024-09-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            9
_cell_length_a                   30.0580(2)
_cell_length_b                   30.0580(2)
_cell_length_c                   45.2905(3)
_cell_measurement_reflns_used    84658
_cell_measurement_temperature    100.02(13)
_cell_measurement_theta_max      51.0370
_cell_measurement_theta_min      1.9620
_cell_volume                     35437.1(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.69a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.69a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.69a (Rigaku OD, 2022)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      100.15
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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     66.00  93.00   0.50    0.80    --   61.94 147.00 141.00   54
  2  \w     77.00 105.00   0.50    0.80    --   61.94 124.00 -24.00   56
  3  \w     37.00 134.00   0.50    0.80    --   61.94  57.00   0.00  194
  4  \w     37.00 137.00   0.50    0.80    --   61.94  57.00 -30.00  200
  5  \w     -6.00  30.00   0.50    0.20    --    0.00  77.00  90.00   72
  6  \w     38.00  73.00   0.50    0.20    --    0.00  77.00  90.00   70
  7  \w     29.00  74.00   0.50    0.20    --    0.00  57.00-180.00   90
  8  \w    -20.00   5.00   0.50    0.20    --    0.00  57.00-180.00   50
  9  \w    -90.00 -65.00   0.50    0.80    --  -52.00 124.00 -24.00   50
 10  \w   -103.00 -78.00   0.50    0.80    --  -52.00 147.00 141.00   50
 11  \w    -13.00  52.00   0.50    0.80    --   61.94 -57.00 -90.00  130
 12  \w    -12.00  63.00   0.50    0.80    --   61.94 -57.00-120.00  150
 13  \w    -11.00  60.00   0.50    0.80    --   61.94 -57.00 -30.00  142
 14  \w    -19.00   6.00   0.50    0.80    --   61.94 -19.00-150.00   50
 15  \w     12.00  38.00   0.50    0.80    --   61.94 -37.00 -90.00   52
 16  \w    -19.00  20.00   0.50    0.80    --   61.94 -19.00 -60.00   78
 17  \w    -18.00  13.00   0.50    0.80    --   61.94 -19.00 -90.00   62
 18  \w    -17.00  22.00   0.50    0.80    --   61.94 -19.00  60.00   78
 19  \w    -10.00  58.00   0.50    0.80    --   61.94 -57.00 120.00  136
 20  \w    -16.00  36.00   0.50    0.80    --   61.94 -37.00 120.00  104
 21  \w    -98.00 -68.00   0.50    0.80    --  -52.00-147.00  91.00   60
 22  \w    -11.00  44.00   0.50    0.20    --    0.00 -99.00 -30.00  110
 23  \w     53.00 108.00   0.50    0.80    --   61.94-147.00  91.00  110
 24  \w     25.00 108.00   0.50    0.80    --   61.94-125.00  30.00  166
 25  \w     33.00 108.00   0.50    0.80    --   61.94-124.00-103.00  150
 26  \w     18.00  84.00   0.50    0.80    --   61.94-125.00-120.00  132
 27  \w     42.00  84.00   0.50    0.80    --   61.94  77.00 150.00   84
 28  \w     -1.00  43.00   0.50    0.20    --    0.00 -99.00-150.00   88
 29  \w    -23.00   2.00   0.50    0.80    --   61.94 -19.00 -90.00   50
 30  \w     35.00  61.00   0.50    0.80    --   61.94  77.00  30.00   52
 31  \w     28.00  74.00   0.50    0.80    --   61.94  77.00   0.00   92
 32  \w     88.00 113.00   0.50    0.80    --   61.94  96.00  82.00   50
 33  \w    -25.00  21.00   0.50    0.20    --    0.00 -57.00  90.00   92
 34  \w    -72.00 -28.00   0.50    0.20    --    0.00 -57.00  90.00   88
 35  \w    -17.00  18.00   0.50    0.20    --   24.00  96.00 -87.77   70
 36  \w    -36.00 -11.00   0.50    0.80    --  -52.00 -91.00 145.96   50
 37  \w    -38.00 -12.00   0.50    0.80    --  -52.00 -89.00 -31.68   52
 38  \w    -41.00 -15.00   0.50    0.80    --  -52.00 -82.00-102.53   52
 39  \w    -40.00 -14.00   0.50    0.80    --  -52.00 -85.00-146.44   52
 40  \w    -41.00 -16.00   0.50    0.80    --  -52.00 -85.00  74.77   50
 41  \w    -41.00 -15.00   0.50    0.80    --  -52.00 -85.00   0.16   52
 42  \w     27.00  92.00   0.50    0.80    --   61.94  77.00 -90.00  130
 43  \w     27.00  88.00   0.50    0.80    --   61.94 -77.00  60.00  122
 44  \w     70.00 137.00   0.50    0.80    --   61.94  78.00 126.14  134
 45  \w     -8.00  23.00   0.50    0.80    --   61.94 -77.00  60.00   62
 46  \w     28.00 103.00   0.50    0.80    --   61.94  78.00  79.02  150
 47  \w     27.00  65.00   0.50    0.80    --   61.94  78.00 126.14   76
 48  \w     27.00 113.00   0.50    0.80    --   61.94  77.00  60.00  172
 49  \w     27.00 122.00   0.50    0.80    --   61.94  77.00-150.00  190
 50  \w     94.00 120.00   0.50    0.80    --   61.94  77.00 -90.00   52
 51  \w     27.00  62.00   0.50    0.80    --   61.94  77.00 -73.35   70
 52  \w     79.00 106.00   0.50    0.80    --   61.94  77.00 -73.35   54
 53  \w     27.00 119.00   0.50    0.80    --   61.94  77.00-173.59  184
 54  \w     -9.00   5.50   0.50    0.80    --   61.94 -57.00  60.00   29
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0470
_diffrn_reflns_av_unetI/netI     0.0233
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       45
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            146901
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        51.217
_diffrn_reflns_theta_max         51.217
_diffrn_reflns_theta_min         1.958
_exptl_absorpt_coefficient_mu    1.006
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.29323
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.69a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    0.778
_exptl_crystal_description       block
_exptl_crystal_F_000             8820
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.113
_refine_diff_density_max         0.561
_refine_diff_density_min         -0.240
_refine_diff_density_rms         0.051
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.11(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1175
_refine_ls_number_reflns         16963
_refine_ls_number_restraints     39
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.0789
_refine_ls_R_factor_gt           0.0722
_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^)+(0.1493P)^2^+51.5653P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2064
_refine_ls_wR_factor_ref         0.2131
_reflns_Friedel_coverage         0.993
_reflns_Friedel_fraction_full    0.990
_reflns_Friedel_fraction_max     0.989
_reflns_number_gt                15874
_reflns_number_total             16963
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03599b2.cif
_cod_data_source_block           9120-hb-100k_auto_sq
_cod_depositor_comments
'Adding full bibliography for 1572552--1572553.cif.'
_cod_original_cell_volume        35437.1(5)
_cod_original_sg_symbol_H-M      'R 3'
_cod_database_code               1572552
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.895
_shelx_estimated_absorpt_t_min   0.872
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.89(3)
 0.11(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups, All N(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C154-O132
 1.45 with sigma of 0.005
 C130-C139
 1.45 with sigma of 0.02
4. Uiso/Uaniso restraints and constraints
C165 \\sim O17 \\sim C195 \\sim C181 \\sim C154 \\sim O132: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
5.a Riding coordinates:
 C163(H16E,H16F,H16G)
5.b Ternary CH refined with riding coordinates:
 C75(H75), C182(H182), C3(H3), C20(H20), C217(H217), C205(H205), C160(H160),
 C171(H171)
5.c Secondary CH2 refined with riding coordinates:
 N208(H20A,H20B), N219(H21A,H21B), N73(H73A,H73B), N196(H19A,H19B), C221(H22A,
 H22B), C172(H17A,H17B), C218(H21C,H21D), C85(H85A,H85B), C199(H19C,H19D),
 C142(H14A,H14B), C167(H16A,H16B), C141(H14C,H14D), C135(H13A,H13B), C169(H16C,
 H16D), C151(H15A,H15B), C185(H18A,H18B), C144(H14E,H14F), C130(H13I,H13J),
 C140(H14G,H14H), C152(H15C,H15D), C137(H13C,H13D), C164(H16H,H16I), C136(H13E,
 H13F), C147(H14I,H14J), C150(H15E,H15F), C154(H15J,H15K), C138(H13G,H13H),
 C139(H13K,H13L), C195(H19E,H19F), C161(H16J,H16K), C165(H16L,H16M), C181(H18C,
 H18D)
5.d Aromatic/amide H refined with riding coordinates:
 N1(H1), N18(H18), C180(H180), N213(H213), N198(H198), C200(H200), C10(H10),
 C61(H61), C192(H192), C206(H206), C8(H8), C77(H77), C211(H211), C222(H222),
 C215(H215), C81(H81), C220(H220), C87(H87), C201(H201), C203(H203), C126(H126),
  C183(H183), C159(H159), C133(H133), C145(H145), C128(H128), C129(H129),
 C156(H156), C143(H143), C157(H157), C175(H175), C170(H170), C168(H168),
 C187(H187), C158(H158), C134(H134), C146(H146), C153(H153), C131(H131),
 C189(H189)
5.e Idealised Me refined as rotating group:
 C177(H17C,H17D,H17E), C155(H15G,H15H,H15I), C179(H17F,H17G,H17H)
;
_shelx_res_checksum              35934
_shelx_hkl_checksum              8168
_shelx_fab_checksum              66103
_platon_squeeze_void_probe_radius 1.20
_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
;