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_1576444
_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         '0.75(C H Cl3), 0.5(C60 H50 O4)'
_chemical_formula_sum            'C30.75 H25.75 Cl2.25 O2'
_chemical_formula_weight         507.02
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2025-06-02
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2025-10-27 deposited with the CCDC.	2026-02-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.763(2)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   19.8054(5)
_cell_length_b                   23.0253(5)
_cell_length_c                   25.2516(6)
_cell_measurement_reflns_used    23153
_cell_measurement_temperature    93
_cell_measurement_theta_max      71.7740
_cell_measurement_theta_min      2.6190
_cell_volume                     11082.3(5)
_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 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.3 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      93
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 5.8140
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.969
_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 -38.00   0.50    3.98    --    5.00  60.00  30.00   92
  2  \w    -84.00 -26.00   0.50    3.98    --    5.00  50.00  60.00  116
  3  \w    -84.00 -38.00   0.50    3.98    --    5.00  60.00 150.00   92
  4  \w    -84.00 -38.00   0.50    3.98    --    5.00  60.00   0.00   92
  5  \w    -84.00 -38.00   0.50    3.98    --    5.00  60.00  60.00   92
  6  \w     14.00  43.00   0.50    3.98    --  -46.80  46.00   3.34   58
  7  \w   -187.00 -38.00   0.50   15.91    --  -97.40  60.00 172.51  298
  8  \w   -187.00  -8.00   0.50   15.91    --  -97.40  14.00 161.11  358
  9  \w   -187.00 -29.00   0.50   15.91    --  -97.40  52.00 179.99  316
 10  \w   -187.00  -8.00   0.50   15.91    --  -97.40   0.00 120.00  358
 11  \w   -187.00 -38.00   0.50   15.91    --  -97.40  60.00 100.33  298
 12  \w   -187.00 -91.00   0.50   15.91    --  -97.40  60.00 107.48  192
 13  \w   -180.00-117.00   0.50   15.91    --  -97.40  47.00  91.19  126
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RCD3): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0254566000
_diffrn_orient_matrix_UB_12      0.0000774000
_diffrn_orient_matrix_UB_13      0.0632436000
_diffrn_orient_matrix_UB_21      -0.0739968000
_diffrn_orient_matrix_UB_22      -0.0178136000
_diffrn_orient_matrix_UB_23      0.0027062000
_diffrn_orient_matrix_UB_31      0.0204982000
_diffrn_orient_matrix_UB_32      -0.0645585000
_diffrn_orient_matrix_UB_33      -0.0006036000
_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  0.0693
_diffrn_reflns_av_unetI/netI     0.0693
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            84896
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         72.813
_diffrn_reflns_theta_min         2.644
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.516
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.78397
_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            'orangish yellow'
_exptl_crystal_colour_modifier   orangish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.216
_exptl_crystal_description       needle
_exptl_crystal_F_000             4232
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.889
_refine_diff_density_min         -0.711
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1285
_refine_ls_number_reflns         21400
_refine_ls_number_restraints     24
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.1139
_refine_ls_R_factor_gt           0.0901
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1631P)^2^+5.1932P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2739
_refine_ls_wR_factor_ref         0.2934
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14230
_reflns_number_total             21400
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09144f2.cif
_cod_data_source_block           221214kk2_auto
_cod_depositor_comments
'Adding full bibliography for 1576439--1576445.cif.'
_cod_database_code               1576444
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_reflns_odcompleteness_completeness 99.57
_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. Rigid bond restraints
 C03Y, C03Z, C040, C044, C045
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
3. Uiso/Uaniso restraints and constraints
C03Y \\sim C03Z \\sim C040 \\sim C045: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 C03Y, C040, C045, C046
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5.a Ternary CH refined with riding coordinates:
 C03H(H10), C03V(H11), C03W(H12)
5.b Aromatic/amide H refined with riding coordinates:
 C00U(H00U), C01G(H01G), C01H(H01H), C01L(H01L), C01P(H01P), C01Q(H01Q),
 C01R(H01R), C01S(H01S), C01T(H01T), C01U(H01U), C029(H029), C02B(H02B),
 C02C(H02C), C02F(H02F), C02G(H02G), C02H(H02H), C02J(H02J), C02L(H02L),
 C02N(H02N), C02O(H02O), C02Q(H02Q), C02R(H02R), C02T(H02T), C02U(H02U),
 C02V(H02V), C02W(H02W), C02X(H02X), C02Y(H02Y), C02Z(H02Z), C030(H030),
 C034(H034), C035(H035), C037(H037), C03A(H1), C03B(H03G), C03C(H2), C03G(H4),
 C03I(H5), C03K(H6)
5.c Idealised Me refined as rotating group:
 C031(H03A,H03B,H03C), C032(H03D,H03E,H03F), C036(H03,H,HA), C03D(H3,HB,HC),
 C03E(H03H,H03I,H03J), C03J(H03K,H03L,H03M), C03N(H03N,H03O,H03P), C03O(H03Q,
 H03R,H03S), C03P(H03T,H03U,H03V), C03R(H7,HD,HE), C03S(H8,HF,HG), C03T(H03W,
 H03X,H03Y), C03U(H03Z,HH,HI), C03Z(H9,HJ,HK), C040(H04A,H04B,H04C), C043(H04D,
 H04E,H04F), C044(H04G,H04H,H04I), C045(H04J,H04K,H04L), C046(H04M,H04N,H04O),
 C047(H04P,H04Q,H04R)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              53224
_shelx_fab_checksum              57745
_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 2.434
_oxdiff_exptl_absorpt_empirical_full_min 0.382