Circularly Polarized Thermally Activated Delayed Fluorescence Emitters in Through-Space Charge Transfer on Asymmetric Spiro Skeletons.
Yang, Sheng-Yi; Wang, Ya-Kun; Peng, Chen-Chen; Wu, Zheng-Guang; Yuan, Shuai; Yu, You-Jun; Li, Hao; Wang, Tong-Tong; Li, Hong-Cheng; Zheng, You-Xuan; Jiang, Zuo-Quan; Liao, Liang-Sheng; Journal of the American Chemical Society 142 (2020) 17756–17765; doi:10.1021/jacs.0c08980

data_4135277
_publ_section_title
;
 Circularly Polarized Thermally Activated Delayed Fluorescence Emitters in
 Through-Space Charge Transfer on Asymmetric Spiro Skeletons.
;
_journal_issue                   41
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              17756
_journal_page_last               17765
_journal_paper_doi               10.1021/jacs.0c08980
_journal_volume                  142
_journal_year                    2020
_chemical_absolute_configuration rm
_chemical_formula_moiety         '2(C52 H32 N4 S), C H Cl3'
_chemical_formula_sum            'C105 H65 Cl3 N8 S2'
_chemical_formula_weight         1609.12
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_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             2020-08-02
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_cell_angle_alpha                88.085(3)
_cell_angle_beta                 79.744(3)
_cell_angle_gamma                73.887(2)
_cell_formula_units_Z            2
_cell_length_a                   10.9982(9)
_cell_length_b                   16.8852(14)
_cell_length_c                   23.750(2)
_cell_measurement_reflns_used    4814
_cell_measurement_temperature    150
_cell_measurement_theta_max      25.956
_cell_measurement_theta_min      2.280
_cell_volume                     4169.0(6)
_computing_cell_refinement       'SAINT V8.40A (?, 2016)'
_computing_data_reduction        'SAINT V8.40A (?, 2016)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.0
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0686
_diffrn_reflns_av_unetI/netI     0.1151
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            43447
_diffrn_reflns_point_group_measured_fraction_full 0.844
_diffrn_reflns_point_group_measured_fraction_max 0.844
_diffrn_reflns_theta_full        25.027
_diffrn_reflns_theta_max         25.027
_diffrn_reflns_theta_min         1.958
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.216
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.7020
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1012 before and 0.0617 after correction. The Ratio of minimum to maximum transmission is 0.9418. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.282
_exptl_crystal_description       block
_exptl_crystal_F_000             1668
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.05
_platon_squeeze_details
;
TITL 0802sfst2_0m_a.res in P1
CELL   10.9982   16.8852   23.7510     88.08     79.74     73.89
SPGR P1
C101 0.972 0.784 0.375 !      18.37 eA-3
C102 0.516 0.326 0.988 !      14.89 eA-3
C103 0.998 0.824 0.487 !      12.99 eA-3
C104 0.092 0.780 0.474 !      10.20 eA-3
C105 0.512 0.261 0.877 !      10.19 eA-3
C106 0.107 0.620 0.420 !       9.12 eA-3
C107 0.754 0.235 0.915 !       8.82 eA-3
C108 0.235 0.715 0.430 !       6.03 eA-3
C109 0.028 0.735 0.437 !       4.47 eA-3
C110 0.579 0.237 0.941 !       3.20 eA-3
Q111 0.501 0.349 0.859 !       2.67 eA-3
C112 0.576 0.298 0.909 !       2.46 eA-3
Q113 0.641 0.312 0.866 !       2.20 eA-3
C114 0.483 0.246 0.937 !       2.06 eA-3
Q115 0.262 0.778 0.331 !       1.77 eA-3
Q116 0.168 0.564 0.458 !       1.72 eA-3
C117 0.077 0.704 0.399 !       1.71 eA-3
Q118 0.362 0.786 0.050 !       1.66 eA-3
C119 0.500 0.288 0.950 !       1.65 eA-3
Q120 0.233 0.783 0.388 !       1.61 eA-3
C121 0.487 0.264 0.984 !       1.60 eA-3
Q122 0.044 0.816 0.373 !       1.60 eA-3
Q123 0.622 0.344 0.873 !       1.58 eA-3
C124 0.028 0.782 0.414 !       1.53 eA-3
C125 0.517 0.300 0.912 !       1.53 eA-3
C126 0.658 0.281 0.905 !       1.53 eA-3
Q127 0.048 0.720 0.503 !       1.52 eA-3
Q128 0.714 0.334 0.841 !       1.50 eA-3
Q129 0.345 0.730 0.164 !       1.49 eA-3
Q130 0.737 0.245 0.960 !       1.45 eA-3
Q131 0.073 0.789 0.425 !       1.43 eA-3
Q132 0.392 0.380 0.952 !       1.42 eA-3
C133 0.590 0.339-0.003 !       1.41 eA-3
Q134 0.078 0.765 0.261 !       1.38 eA-3
Q135 0.063 0.719 0.247 !       1.38 eA-3
Q136 0.794 0.334 0.858 !       1.37 eA-3
Q137 0.094 0.848 0.450 !       1.35 eA-3
Q138 0.626 0.356 0.910 !       1.32 eA-3
Q139 0.406 0.706 0.384 !       1.31 eA-3
Q140 0.830 0.235 0.654 !       1.30 eA-3
C141 0.635 0.280 0.968 !       1.27 eA-3
Q142 0.612 1.002 0.913 !       1.27 eA-3
Q143 0.669 0.235 0.974 !       1.27 eA-3
Q144 0.873 0.857 0.508 !       1.23 eA-3
Q145 0.785 0.285 0.842 !       1.23 eA-3
Q146 0.325 0.688 0.422 !       1.23 eA-3
Q147 0.503 0.154 0.894 !       1.22 eA-3
Q148 0.094 0.638 0.371 !       1.21 eA-3
Q149 0.877 0.687 0.374 !       1.19 eA-3
Q150 0.593 0.411 0.001 !       1.19 eA-3
Q151 0.032 0.817 0.442 !       1.18 eA-3
Q152 0.403 0.203 0.901 !       1.18 eA-3
C153 0.862 0.216 0.901 !       1.18 eA-3
Q154 0.830 0.266 0.948 !       1.15 eA-3
Q155 0.207 0.423 0.393 !       1.14 eA-3
Q156 0.217 0.626 0.393 !       1.14 eA-3
Q157 0.160 0.526 0.425 !       1.14 eA-3
Q158 0.482 0.329 0.824 !       1.11 eA-3
Q159 0.127 0.796 0.394 !       1.10 eA-3
Q160 0.375 0.654 0.378 !       1.09 eA-3
Q161 0.084 0.582 0.447 !       1.08 eA-3
Q162 0.294 0.795 0.415 !       1.07 eA-3
Q163 1.000 0.612 0.432 !       1.06 eA-3
Q164 0.426 0.142 0.886 !       1.06 eA-3
C165 0.090 0.790 0.524 !       1.05 eA-3
Q166 0.748 0.188 0.871 !       1.04 eA-3
Q167 0.159 0.583 0.372 !       1.04 eA-3
Q168 1.002 0.181 0.363 !       1.03 eA-3
Q169 0.584 0.184 0.819 !       1.03 eA-3
Q170 0.610 0.202 0.857 !       1.03 eA-3
Q171 0.624 0.298 0.807 !       1.02 eA-3
Q172 0.040 0.870 0.483 !       1.02 eA-3
Q173 0.559 0.273 0.830 !       1.01 eA-3
Q174 0.173 0.816 0.315 !       1.01 eA-3
C175 0.592 0.312 0.022 !       1.00 eA-3
Q176 0.939 0.818 0.423 !       1.00 eA-3
C177 0.576 0.265 0.025 !       1.00 eA-3
Q178 0.155 0.483 0.402 !       1.00 eA-3
C179 0.942 0.721 0.380 !       0.98 eA-3
Q180 0.941 0.672 0.420 !       0.98 eA-3
Q181 0.380 0.246 0.002 !       0.97 eA-3
Q182 0.236 0.863 0.424 !       0.97 eA-3
Q183 0.483 0.215 0.971 !       0.96 eA-3
Q184 0.608 0.248 0.055 !       0.96 eA-3
Q185 0.421 0.654 0.388 !       0.96 eA-3
Q186 0.328 0.739 0.354 !       0.95 eA-3
Q187 0.330 0.244 0.864 !       0.95 eA-3
Q188 0.407 0.263 0.274 !       0.94 eA-3
Q189 0.089 0.170 0.516 !       0.94 eA-3
Q190 0.981 0.876 0.375 !       0.93 eA-3
Q191 0.312 0.784 0.450 !       0.93 eA-3
Q192 0.657 0.415 0.906 !       0.93 eA-3
Q193 0.756 0.317 0.991 !       0.92 eA-3
Q194 0.159 0.708 0.220 !       0.92 eA-3
Q195 0.834 0.241 0.866 !       0.92 eA-3
Q196 0.781 0.916 0.799 !       0.91 eA-3
Q197 0.829 0.139 0.050 !       0.90 eA-3
Q198 0.270 0.828 0.473 !       0.90 eA-3
Q199 0.076 0.857 0.506 !       0.89 eA-3
;
_refine_diff_density_max         0.819
_refine_diff_density_min         -0.607
_refine_diff_density_rms         0.075
_refine_ls_abs_structure_details
;
 Flack x determined using 3984 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.09(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2161
_refine_ls_number_reflns         24861
_refine_ls_number_restraints     4558
_refine_ls_restrained_S_all      0.947
_refine_ls_R_factor_all          0.1570
_refine_ls_R_factor_gt           0.0904
_refine_ls_shift/su_max          0.011
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1281P)^2^+5.0045P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2195
_refine_ls_wR_factor_ref         0.2716
_reflns_Friedel_coverage         0.696
_reflns_Friedel_fraction_full    0.693
_reflns_Friedel_fraction_max     0.693
_reflns_number_gt                14157
_reflns_number_total             24861
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja0c08980_si_004.cif
_cod_data_source_block           0802sfst2_0m_sq
_cod_depositor_comments
'Adding full bibliography for 4135274--4135279.cif.'
_cod_original_cell_volume        4169.1(6)
_cod_database_code               4135277
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.989
_shelx_estimated_absorpt_t_min   0.968
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 C160-C159 \\sim C161-C159 \\sim C163-C160 \\sim C162-C161 \\sim C162-C164
\\sim C163-C164
 with sigma of 0.02
 Cl5-C156 \\sim Cl4-C156 \\sim Cl7-C156 \\sim Cl6-C156
 with sigma of 0.02
3. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08
Uanis(C161) \\sim Ueq, Uanis(C159) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Fixed Sof: Cl6(0.8) Cl4(0.8) H15A(0.5) H159(0.5) H156(0.8) H15B(0.2)
 C161(0.5) H161(0.5) C162(0.5) H162(0.5) C163(0.5) H163(0.5) C160(0.5)
 H160(0.5) Cl5(0.2) Cl7(0.2)
7.a Ternary CH refined with riding coordinates:
 C155(H155), C156(H156), C156(H15B)
7.b Aromatic/amide H refined with riding coordinates:
 C111(H111), C175(H175), C140(H140), C193(H193), C174(H174), C131(H131),
 C209(H209), C196(H196), C112(H112), C122(H122), C136(H136), C124(H124),
 C91(H91), C133(H133), C177(H177), C208(H208), C77(H77), C194(H194), C19(H19),
 C73(H73), C88(H88), C121(H121), C113(H113), C95(H95), C70(H70), C96(H96),
 C1(H1), C139(H139), C12(H12), C4(H4), C180(H180), C11(H11), C75(H75), C90(H90),
  C170(H170), C182(H182), C151(H151), C105(H105), C178(H178), C207(H207),
 C100(H100), C154(H154), C89(H89), C32(H32), C5(H5), C181(H181), C14(H14),
 C36(H36), C69(H69), C72(H72), C29(H29), C10(H10), C191(H191), C125(H125),
 C190(H190), C81(H81), C21(H21), C04F(H04F), C18(H18), C195(H195), C146(H146),
 C76(H76), C153(H153), C17(H17), C120(H120), C199(H199), C150(H150), C31(H31),
 C137(H137), C64(H64), C84(H84), C3(H3), C189(H189), C126(H126), C25(H25),
 C26(H26), C66(H66), C152(H152), C83(H83), C119(H119), C106(H106), C132(H132),
 C2(H2), C27(H27), C38(H38), C52(H52), C30(H30), C102(H102), C82(H82),
 C201(H201), C65(H65), C200(H200), C127(H127), C63(H63), C101(H101), C145(H145),
  C188(H188), C57(H57), C51(H51), C37(H37), C13(H13), C107(H107), C62(H62),
 C103(H103), C148(H148), C147(H147), C171(H171), C58(H58), C144(H144), C56(H56),
  C43(H43), C50(H50), C39(H39), C42(H42), C06B(H06B), C157(H157), C108(H108),
 C202(H202), C44(H44), C55(H55), C158(H158), C172(H172), C168(H168), C169(H169),
  C45(H45), C159(H15A), C159(H159), C161(H161), C162(H162), C163(H163),
 C160(H160)
;
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'