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_1576441
_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_absolute_configuration unk
_chemical_formula_moiety         'C H Cl3, C34 H22 O2'
_chemical_formula_sum            'C35 H23 Cl3 O2'
_chemical_formula_weight         581.88
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-01-17
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2025-10-28 deposited with the CCDC.	2026-02-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 116.469(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.3054(3)
_cell_length_b                   17.9492(3)
_cell_length_c                   12.5807(3)
_cell_measurement_reflns_used    14169
_cell_measurement_temperature    93
_cell_measurement_theta_max      71.9990
_cell_measurement_theta_min      4.5830
_cell_volume                     2689.59(12)
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_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 0.998
_diffrn_measured_fraction_theta_max 0.983
_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  94.00   0.50    0.50    --    5.00   0.00   0.00  356
  2  \w    -84.00 -38.00   0.50    0.50    --    5.00  60.00  30.00   92
  3  \w    -84.00  94.00   0.50    0.50    --    5.00   0.00   0.00  356
  4  \w      4.00  42.00   0.50    0.50    --  -46.90  44.00  15.62   76
  5  \w   -187.00 -26.00   0.50    0.50    --  -97.40  50.00  -1.77  322
  6  \w   -187.00 -38.00   0.50    0.50    --  -97.40  60.00 179.51  298
  7  \w   -144.00 -32.00   0.50    0.50    --  -97.40  52.00  -4.79  224
  8  \w   -186.00 -36.00   0.50    0.50    --  -97.40  58.00 108.02  300
  9  \w   -124.00 -38.00   0.50    0.50    --  -97.40  58.00 126.52  172
 10  \w   -185.00-100.00   0.50    0.50    --  -97.40  31.00  70.84  170
 11  \w   -179.00 -35.00   0.50    0.50    --  -97.40  55.00 167.90  288
;
_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      0.0121189000
_diffrn_orient_matrix_UB_12      -0.0664231000
_diffrn_orient_matrix_UB_13      -0.0710095000
_diffrn_orient_matrix_UB_21      -0.1287415000
_diffrn_orient_matrix_UB_22      -0.0051346000
_diffrn_orient_matrix_UB_23      -0.0698679000
_diffrn_orient_matrix_UB_31      0.0025032000
_diffrn_orient_matrix_UB_32      0.0541211000
_diffrn_orient_matrix_UB_33      -0.0938186000
_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  0.0886
_diffrn_reflns_av_unetI/netI     0.0461
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            19869
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.189
_diffrn_reflns_theta_min         4.455
_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    3.345
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.38372
_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 yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.437
_exptl_crystal_description       block
_exptl_crystal_F_000             1200
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.973
_refine_diff_density_min         -0.751
_refine_diff_density_rms         0.081
_refine_ls_extinction_coef       0.00066(19)
_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   1.076
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     364
_refine_ls_number_reflns         5211
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0593
_refine_ls_R_factor_gt           0.0567
_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^)+(0.1022P)^2^+2.0188P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1649
_refine_ls_wR_factor_ref         0.1677
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4765
_reflns_number_total             5211
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09144f2.cif
_cod_data_source_block           250117kk_auto
_cod_depositor_comments
'Adding full bibliography for 1576439--1576445.cif.'
_cod_database_code               1576441
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C34H22O2
_shelx_estimated_absorpt_t_max   0.554
_shelx_estimated_absorpt_t_min   0.554
_reflns_odcompleteness_completeness 99.84
_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 Ternary CH refined with riding coordinates:
 C014(H014)
2.b Aromatic/amide H refined with riding coordinates:
 C00E(H00E), C00J(H00J), C00M(H00M), C00O(H00O), C00Q(H00Q), C00R(H00R),
 C00S(H00S), C00U(H00U), C00V(H00V), C00W(H00W), C00X(H00X), C00Y(H00Y),
 C00Z(H00Z), C010(H010), C011(H011), C013(H013)
2.c Idealised Me refined as rotating group:
 C00T(H00A,H00B,H00C), C012(H01A,H01B,H01C)
;
_shelx_res_checksum              11391
_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 2.296
_oxdiff_exptl_absorpt_empirical_full_min 0.632