Self-induced charge transfer activation enables metal-free C-H coupling of polycyclic aromatic hydrocarbons under photo irradiation.
Kurokawa, Kazuma; Kohyama, Aki; Kuroda, Yusuke; Tao-Kakuyama, Keisuke; Takikawa, Hiroshi; Takasu, Kiyosei; Chemical science 17 (2026) 4942–4947; doi:10.1039/d5sc09144f

data_1576445
_publ_section_title
;
 Self-induced charge transfer activation enables metal-free C-H coupling
 of polycyclic aromatic hydrocarbons under photo irradiation.
;
_journal_issue                   10
_journal_name_full               'Chemical science'
_journal_page_first              4942
_journal_page_last               4947
_journal_paper_doi               10.1039/d5sc09144f
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C60 H44 F6 O8 S2'
_chemical_formula_sum            'C60 H44 F6 O8 S2'
_chemical_formula_weight         1071.07
_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     iterative
_audit_creation_date             2024-11-13
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2025-10-27 deposited with the CCDC.	2026-02-06 downloaded from the CCDC.
;
_cell_angle_alpha                97.562(3)
_cell_angle_beta                 99.303(3)
_cell_angle_gamma                91.481(3)
_cell_formula_units_Z            2
_cell_length_a                   11.2328(4)
_cell_length_b                   11.3152(5)
_cell_length_c                   24.1172(8)
_cell_measurement_reflns_used    15207
_cell_measurement_temperature    93
_cell_measurement_theta_max      71.9200
_cell_measurement_theta_min      3.7480
_cell_volume                     2995.2(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.122a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.3-ac4 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      93
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_detector_type            'Rigaku Saturn724+'
_diffrn_measured_fraction_theta_full 0.974
_diffrn_measured_fraction_theta_max 0.905
_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    -84.00 -26.00   0.50    1.17    --    5.00  50.00  60.00  116
  2  \w    -84.00 -26.00   0.50    1.17    --    5.00  50.00 150.00  116
  3  \w    -84.00 -38.00   0.50    1.17    --    5.00  60.00   0.00   92
  4  \w    -84.00 -26.00   0.50    1.17    --    5.00  50.00   0.00  116
  5  \w   -136.00 -38.00   0.50    1.17    --  -46.90  60.00 120.00  196
  6  \w   -136.00 -34.00   0.50    1.17    --  -46.90  57.00 176.30  204
  7  \w   -187.00  -8.00   0.50    4.68    --  -97.40  10.00 120.00  358
  8  \w   -187.00 -37.00   0.50    4.68    --  -97.40  59.00  44.14  300
  9  \w   -187.00 -38.00   0.50    4.68    --  -97.40  60.00 179.88  298
 10  \w   -187.00 -29.00   0.50    4.68    --  -97.40  52.00  -2.89  316
 11  \w   -187.00  -8.00   0.50    4.68    --  -97.40  40.00   0.00  358
 12  \w   -187.00  -8.00   0.50    4.68    --  -97.40  11.00  -4.57  358
 13  \w   -187.00 -68.00   0.50    4.68    --  -97.40  60.00 128.33  238
 14  \w   -103.00 -30.00   0.50    4.68    --  -97.40  53.00  -6.90  146
 15  \w   -187.00-161.00   0.50    4.68    --  -97.40  53.00  -6.90   52
 16  \w   -161.00 -47.00   0.50    4.68    --  -97.40  60.00  33.58  228
 17  \w   -187.00 -32.00   0.50    4.68    --  -97.40  41.00 177.90  310
 18  \w   -168.00-135.00   0.50    4.68    --  -97.40  58.00 177.71   66
 19  \w   -159.00 -57.00   0.50    4.68    --  -97.40  60.00  81.27  204
 20  \w   -187.00 -95.00   0.50    4.68    --  -97.40  60.00  -7.69  184
 21  \w    -34.00  -9.00   0.50    4.68    --  -97.40  45.00  -8.11   50
 22  \w   -187.00 -95.00   0.50    4.68    --  -97.40  45.00  -8.11  184
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RCD3): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'Mitegen 50um'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0181930000
_diffrn_orient_matrix_UB_12      -0.0227629000
_diffrn_orient_matrix_UB_13      -0.0624047000
_diffrn_orient_matrix_UB_21      -0.1268178000
_diffrn_orient_matrix_UB_22      0.0443158000
_diffrn_orient_matrix_UB_23      -0.0187356000
_diffrn_orient_matrix_UB_31      0.0542724000
_diffrn_orient_matrix_UB_32      0.1281614000
_diffrn_orient_matrix_UB_33      0.0050449000
_diffrn_radiation_collimation    0.3
_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  0.0845
_diffrn_reflns_av_unetI/netI     0.0652
_diffrn_reflns_Laue_measured_fraction_full 0.974
_diffrn_reflns_Laue_measured_fraction_max 0.905
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -29
_diffrn_reflns_number            41223
_diffrn_reflns_point_group_measured_fraction_full 0.974
_diffrn_reflns_point_group_measured_fraction_max 0.905
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         75.775
_diffrn_reflns_theta_min         3.750
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_current           24.0
_diffrn_source_power             1.2
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    1.388
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.41583
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.122a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.188
_exptl_crystal_description       block
_exptl_crystal_F_000             1108
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.633
_refine_diff_density_min         -0.658
_refine_diff_density_rms         0.089
_refine_ls_extinction_coef       0.0012(3)
_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   0.849
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     694
_refine_ls_number_reflns         11291
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.849
_refine_ls_R_factor_all          0.1112
_refine_ls_R_factor_gt           0.0877
_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^)+(0.1793P)^2^+7.9250P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2568
_refine_ls_wR_factor_ref         0.2774
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7976
_reflns_number_total             11291
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09144f2.cif
_cod_data_source_block           231218kk2_auto
_cod_depositor_comments
'Adding full bibliography for 1576439--1576445.cif.'
_cod_database_code               1576445
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C60H44F6O8S2
_shelx_estimated_absorpt_t_max   0.681
_shelx_estimated_absorpt_t_min   0.681
_reflns_odcompleteness_completeness 97.48
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C46(H46), C40(H40), C23(H23), C34(H34), C37(H37), C20(H20), C45(H45),
 C43(H43), C39(H39), C14(H14), C38(H38), C8(H8), C30(H30), C13(H13), C11(H11),
 C5(H5), C7(H7), C21(H21), C6(H6), C29(H29)
2.b Idealised Me refined as rotating group:
 C62(H62A,H62B,H62C), C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C72(H72A,H72B,
 H72C), C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C52(H52A,H52B,H52C), C76(H76A,
 H76B,H76C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              85436
_shelx_fab_checksum              44664
_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 2.067
_oxdiff_exptl_absorpt_empirical_full_min 0.567