Stereoselective synthesis of heterocyclic tetraphenylethylene analogues with configuration-dependent solid-state luminescence
Seinfeld, Mathilde; Rouillon, Jean; Rullan, Raphael; Jeanneau, Erwann; Steinmann, Stephan N.; Andraud, Chantal; Le Bahers, Tangui; Monnereau, Cyrille; Chemical Science 16 (2025) 10523–10531; doi:10.1039/D4SC08333D

data_1574575
_publ_section_title
;
 Stereoselective synthesis of heterocyclic tetraphenylethylene analogues
 with configuration-dependent solid-state luminescence
;
_journal_issue                   23
_journal_name_full               'Chemical Science'
_journal_page_first              10523
_journal_page_last               10531
_journal_paper_doi               10.1039/D4SC08333D
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C56 H44 N8, 2(C6 H12)'
_chemical_formula_sum            'C68 H68 N8'
_chemical_formula_weight         997.30
_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             2024-02-02
_audit_creation_method
;
Olex2 1.5-ac6-015
(compiled 2023.12.04 svn.r209d9fb2 for Rigaku Oxford Diffraction, GUI svn.r6873)
;
_audit_update_record
;
2024-11-28 deposited with the CCDC.	2025-05-05 downloaded from the CCDC.
;
_cell_angle_alpha                78.9860(10)
_cell_angle_beta                 81.9550(10)
_cell_angle_gamma                71.4680(10)
_cell_formula_units_Z            1
_cell_length_a                   7.77940(10)
_cell_length_b                   9.85000(10)
_cell_length_c                   18.6746(2)
_cell_measurement_reflns_used    35582
_cell_measurement_temperature    99.9(2)
_cell_measurement_theta_max      78.0490
_cell_measurement_theta_min      4.7820
_cell_volume                     1326.95(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.105a 64-bit (release 11-01-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.105a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-ac6-015 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-015 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.9(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.930
_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     17.00  79.00   0.50    0.20    --   47.49 -98.00-165.00  124
  2  \w    -67.00   5.00   0.50    0.20    --  -48.74  98.00 -58.00  144
  3  \w    -67.00 -16.00   0.50    0.62    --  -84.50  98.00 -58.00  102
  4  \w   -153.00-102.00   0.50    0.62    --  -84.50 -98.00-165.00  102
  5  \w     32.00  92.00   0.50    0.62    --  100.60 -98.00-165.00  120
  6  \w    123.00 169.00   0.50    0.62    --  100.60  98.00 -58.00   92
  7  \w    123.00 178.00   0.50    0.62    --  111.29  98.00 -58.00  110
  8  \w     43.00  93.00   0.50    0.62    --  111.29 -98.00-165.00  100
  9  \w      3.00  38.00   0.50    0.20    --   16.00  67.00 105.23   70
 10  \w      7.00  40.00   0.50    0.20    --   20.00  66.00 170.67   66
 11  \w     20.00  47.00   0.50    0.20    --   32.00  63.00 -48.23   54
 12  \w    -30.00  19.00   0.50    0.20    --   47.49 -38.00 120.00   98
 13  \w   -126.00 -40.00   0.50    0.20    --  -48.74 -38.00 150.00  172
 14  \w   -126.00 -40.00   0.50    0.20    --  -48.74 -38.00 150.00  172
 15  \w   -131.00 -47.00   0.50    0.20    --  -56.00 -51.00-107.17  168
 16  \w   -152.00-102.00   0.50    0.62    --  -84.50 -95.00-150.00  100
 17  \w   -157.00 -87.00   0.50    0.62    --  -84.50 -61.00  30.00  140
 18  \w    -51.00 -11.00   0.50    0.62    --  -84.50  61.00-120.00   80
 19  \w    -51.00 -11.00   0.50    0.62    --  -84.50  61.00 -60.00   80
 20  \w   -151.00-102.00   0.50    0.62    --  -84.50 -77.00 -30.00   98
 21  \w    -51.00 -11.00   0.50    0.62    --  -84.50  61.00  90.00   80
 22  \w   -169.00 -84.00   0.50    0.62    --  -92.25 -46.00 -90.42  170
 23  \w     33.00  92.00   0.50    0.62    --  100.60 -95.00  30.00  118
 24  \w     33.00  92.00   0.50    0.62    --  100.60 -95.00 120.00  118
 25  \w     34.00 100.00   0.50    0.62    --  100.60-125.00 120.00  132
 26  \w    109.00 174.00   0.50    0.62    --  100.60  61.00-180.00  130
 27  \w     33.00  92.00   0.50    0.62    --  100.60 -95.00 -60.00  118
 28  \w     33.00  92.00   0.50    0.62    --  100.60 -95.00 150.00  118
 29  \w     34.00  75.00   0.50    0.62    --  100.60 -77.00  60.00   82
 30  \w     34.00 100.00   0.50    0.62    --  100.60-125.00 120.00  132
 31  \w     44.00  92.00   0.50    0.62    --  111.29 -95.00-120.00   96
 32  \w     44.00  75.00   0.50    0.62    --  111.29 -77.00-120.00   62
 33  \w     85.00 136.00   0.50    0.62    --  111.29  15.00   0.00  102
 34  \w    112.00 178.00   0.50    0.62    --  111.29 125.00-120.00  132
 35  \w     85.00 136.00   0.50    0.62    --  111.29  15.00 -90.00  102
 36  \w     85.00 136.00   0.50    0.62    --  111.29  15.00 150.00  102
 37  \w    112.00 178.00   0.50    0.62    --  111.29 125.00 120.00  132
 38  \w     40.00 101.00   0.50    0.62    --  111.29-125.00 -90.00  122
 39  \w     44.00  75.00   0.50    0.62    --  111.29 -77.00   0.00   62
 40  \w     12.00  43.00   0.50    0.20    --   24.00  65.00 -17.56   62
 41  \w     16.00  47.00   0.50    0.20    --   28.00  63.00-100.58   62
 42  \w     25.00  54.00   0.50    0.20    --   36.00  61.00  57.18   58
 43  \w     29.00  59.00   0.50    0.20    --   40.00  58.00  -0.27   60
 44  \w     33.00  59.00   0.50    0.20    --   44.00  59.00  81.05   52
 45  \w   -135.00 -51.00   0.50    0.20    --  -60.00 -51.00  69.98  168
 46  \w   -144.00 -59.00   0.50    0.20    --  -68.00 -50.00 108.86  170
 47  \w   -144.00 -59.00   0.50    0.20    --  -68.00 -49.00-148.64  170
 48  \w   -147.00 -63.00   0.50    0.20    --  -72.00 -51.00  16.12  168
 49  \w   -148.00 -63.00   0.50    0.20    --  -72.00 -48.00 -29.49  170
 50  \w   -148.00 -63.00   0.50    0.20    --  -72.00 -49.00  36.07  170
 51  \w   -151.00 -66.00   0.50    0.20    --  -76.00 -52.00-120.18  170
 52  \w   -156.00 -71.00   0.50    0.62    --  -80.00 -50.00 -57.93  170
 53  \w   -155.00 -70.00   0.50    0.62    --  -80.00 -52.00  -0.07  170
 54  \w   -156.00 -72.00   0.50    0.62    --  -80.00 -45.00 -46.21  168
 55  \w   -155.00 -71.00   0.50    0.62    --  -80.00 -51.00 147.66  168
 56  \w   -159.00 -74.00   0.50    0.62    --  -84.00 -52.00 -78.10  170
 57  \w   -159.00 -74.00   0.50    0.62    --  -84.00 -52.00 175.69  170
 58  \w   -159.00 -74.00   0.50    0.62    --  -84.00 -52.00-165.14  170
 59  \w   -164.00 -79.00   0.50    0.62    --  -88.00 -49.00-116.52  170
 60  \w   -167.00 -83.00   0.50    0.62    --  -92.25 -53.00  29.86  168
 61  \w   -167.00 -83.00   0.50    0.62    --  -92.25 -55.00 139.42  168
 62  \w   -167.00 -83.00   0.50    0.62    --  -92.25 -55.00-130.24  168
 63  \w   -167.00 -83.00   0.50    0.62    --  -92.25 -54.00 106.96  168
 64  \w   -167.00 -83.00   0.50    0.62    --  -92.25 -55.00  52.90  168
 65  \w   -166.00 -83.00   0.50    0.62    --  -92.25 -57.00  67.65  166
 66  \w   -166.00 -83.00   0.50    0.62    --  -92.25 -57.00  84.68  166
 67  \w   -167.00 -83.00   0.50    0.62    --  -92.25 -55.00 170.79  168
 68  \w   -166.00 -84.00   0.50    0.62    --  -92.25 -58.00  -3.31  164
 69  \w   -168.00 -83.00   0.50    0.62    --  -92.25 -50.00 -56.98  170
 70  \w   -166.00 -83.00   0.50    0.62    --  -92.25 -57.00 124.16  166
 71  \w     90.00 166.00   0.50    0.62    --  100.60  30.00  60.00  152
 72  \w     20.00  49.00   0.50    0.20    --   32.00  62.00-140.48   58
 73  \w     25.00  57.00   0.50    0.20    --   36.00  60.00 132.31   64
 74  \w     29.00  57.00   0.50    0.20    --   40.00  60.00 -53.79   56
 75  \w     29.00  59.00   0.50    0.20    --   40.00  59.00  24.72   60
 76  \w     29.00  57.00   0.50    0.20    --   40.00  60.00 168.77   56
 77  \w     29.00  57.00   0.50    0.20    --   40.00  60.00 111.79   56
 78  \w     38.00 123.00   0.50    0.20    --   47.49  51.00 -97.19  170
 79  \w   -135.00 -50.00   0.50    0.20    --  -60.00 -52.00 160.45  170
 80  \w   -147.00 -63.00   0.50    0.20    --  -72.00 -51.00 104.53  168
 81  \w   -156.00-103.00   0.50    0.62    --  -80.00 -45.00  58.34  106
 82  \w   -159.00 -74.00   0.50    0.62    --  -84.00 -52.00-156.61  170
 83  \w    -51.00 -11.00   0.50    0.62    --  -84.50  61.00-180.00   80
 84  \w   -166.00 -83.00   0.50    0.62    --  -92.25 -56.00  98.51  166
 85  \w   -166.00 -84.00   0.50    0.62    --  -92.25 -59.00 157.42  164
 86  \w     34.00  75.00   0.50    0.62    --  100.60 -77.00 -60.00   82
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1165204000
_diffrn_orient_matrix_UB_12      -0.1537384000
_diffrn_orient_matrix_UB_13      0.0299461000
_diffrn_orient_matrix_UB_21      -0.0010131000
_diffrn_orient_matrix_UB_22      0.0491176000
_diffrn_orient_matrix_UB_23      0.0736266000
_diffrn_orient_matrix_UB_31      -0.1742507000
_diffrn_orient_matrix_UB_32      -0.0429179000
_diffrn_orient_matrix_UB_33      0.0282347000
_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  0.0252
_diffrn_reflns_av_unetI/netI     0.0127
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.930
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            49438
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.930
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         78.304
_diffrn_reflns_theta_min         4.794
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.568
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68509
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.105a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.248
_exptl_crystal_description       plate
_exptl_crystal_F_000             532
_exptl_crystal_size_max          0.231
_exptl_crystal_size_mid          0.148
_exptl_crystal_size_min          0.073
_refine_diff_density_max         0.658
_refine_diff_density_min         -0.371
_refine_diff_density_rms         0.047
_refine_ls_extinction_coef       0.0014(4)
_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   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     344
_refine_ls_number_reflns         5300
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0481
_refine_ls_R_factor_gt           0.0461
_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^)+(0.0593P)^2^+0.7939P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1206
_refine_ls_wR_factor_ref         0.1223
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4972
_reflns_number_total             5300
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc08333d1.cif
_cod_data_source_block           (E)-DTS-2
_cod_depositor_comments
'Adding full bibliography for 1574574--1574575.cif.'
_cod_database_code               1574575
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C68 H68 N8 '
_shelx_estimated_absorpt_t_max   0.960
_shelx_estimated_absorpt_t_min   0.880
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B), C32(H32A,H32B),
 C33(H33A,H33B), C34(H34A,H34B)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C6(H6), C7(H7), C8(H8), C9(H9), C10(H10), C12(H12), C13(H13),
 C15(H15), C16(H16), C18(H18), C19(H19), C20(H20), C21(H21), C22(H22), C24(H24),
  C25(H25), C26(H26), C27(H27), C28(H28)
;
_shelx_res_checksum              71888
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in perfluoroether oil'
_olex2_submission_original_sample_id DTS-DPA-BzZ
_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 1.311
_oxdiff_exptl_absorpt_empirical_full_min 0.713