Multiple effects of aromatic substituents on excited-state properties and singlet fission process in azaquinodimethane systems.
Zhao, Zhenxiang; Wang, Senhao; Shi, Xiaomei; Fu, Hongbing; Wang, Long; Chemical science 16 (2025) 5565–5572; doi:10.1039/d4sc06494a

data_1573938
_publ_section_title
;
 Multiple effects of aromatic substituents on excited-state properties and
 singlet fission process in azaquinodimethane systems.
;
_journal_issue                   13
_journal_name_full               'Chemical science'
_journal_page_first              5565
_journal_page_last               5572
_journal_paper_doi               10.1039/d4sc06494a
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C34 H34 N2 O2 S2'
_chemical_formula_sum            'C34 H34 N2 O2 S2'
_chemical_formula_weight         566.75
_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             2023-03-04
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6439)
;
_audit_update_record
;
2024-08-31 deposited with the CCDC.	2025-02-17 downloaded from the CCDC.
;
_cell_angle_alpha                77.396(5)
_cell_angle_beta                 89.959(6)
_cell_angle_gamma                64.379(8)
_cell_formula_units_Z            4
_cell_length_a                   11.0327(10)
_cell_length_b                   12.2831(8)
_cell_length_c                   24.7672(12)
_cell_measurement_reflns_used    5173
_cell_measurement_temperature    149(2)
_cell_measurement_theta_max      71.1280
_cell_measurement_theta_min      3.6810
_cell_volume                     2936.6(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_collection       'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_data_reduction        'CrysAlisPro 1.171.39.33c (Rigaku OD, 2017)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149(2)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.987
_diffrn_measured_fraction_theta_max 0.987
_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     97.00 126.00   0.50    0.50    --   42.30  77.00 120.00   58
  2  \w      4.00  66.00   0.50    0.50    --   42.30  38.00  30.00  124
  3  \w     87.00 115.00   0.50    0.50    --   42.30  77.00 150.00   56
  4  \w     89.00 130.00   0.50    0.50    --   42.30  77.00-120.00   82
  5  \w     80.00 130.00   0.50    0.50    --   42.30  77.00-150.00  100
  6  \w    -40.00  71.00   0.50    0.50    --   42.30 -57.00  30.00  222
  7  \w     45.00 178.00   0.50    0.80    --  101.60 -25.00-180.00  266
  8  \w     13.00 141.00   0.50    0.80    --  101.60 -82.00  60.00  256
  9  \w    152.00 179.00   0.50    0.80    --  101.60  38.00-180.00   54
 10  \w     29.00  55.00   0.50    0.80    --  101.60 -82.00   0.00   52
 11  \w     92.00 117.00   0.50    0.80    --  101.60 -82.00   0.00   50
 12  \w     16.00 134.00   0.50    0.80    --  101.60 -63.00  60.00  236
 13  \w     16.00 148.00   0.50    0.80    --  101.60 -38.00-180.00  264
 14  \w     51.00 100.00   0.50    0.80    --  101.60 -82.00  30.00   98
 15  \w    160.00 186.00   0.50    0.80    --  101.60  82.00-120.00   52
 16  \w    120.00 146.00   0.50    0.80    --  101.60  38.00-180.00   52
 17  \w     99.00 125.00   0.50    0.80    --  101.60 -82.00 -30.00   52
 18  \w     72.00  97.00   0.50    0.80    --  101.60  38.00-180.00   50
 19  \w     24.00  84.00   0.50    0.50    --   42.10 -82.00-120.00  120
 20  \w    -47.00  55.00   0.50    0.50    --   42.10 -57.00-150.00  204
 21  \w     53.00  87.00   0.50    0.50    --   42.10  57.00  90.00   68
 22  \w     17.00  43.00   0.50    0.50    --   42.10  57.00  90.00   52
 23  \w    -26.00  82.00   0.50    0.50    --   42.10 -82.00-180.00  216
 24  \w     12.00  57.00   0.50    1.00    --  101.60 -12.00 120.00   90
 25  \w     66.00 144.00   0.50    1.00    --  101.60 -82.00-120.00  156
 26  \w     73.00 125.00   0.50    1.00    --  101.60 -82.00 150.00  104
 27  \w     13.00  38.00   0.50    1.00    --  101.60 -82.00-120.00   50
 28  \w     64.00 117.00   0.50    1.00    --  101.60 -82.00 -90.00  106
 29  \w     74.00 118.00   0.50    1.00    --  101.60 -82.00 -60.00   88
 30  \w     82.00 127.00   0.50    1.00    --  101.60 -63.00 120.00   90
 31  \w     30.00  60.00   0.50    1.00    --  101.60  25.00 120.00   60
 32  \w     66.00 169.00   0.50    1.00    --  101.60  25.00 120.00  206
 33  \w     20.00  64.00   0.50    1.00    --  101.60 -63.00 120.00   88
 34  \w     92.00 165.00   0.50    1.00    --  101.60 -12.00 120.00  146
 35  \w     16.00  67.00   0.50    1.00    --  101.60 -38.00 -30.00  102
 36  \w     80.00 108.00   0.50    1.00    --  101.60 -82.00  90.00   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0846556000
_diffrn_orient_matrix_UB_12      0.1380311000
_diffrn_orient_matrix_UB_13      -0.0002231000
_diffrn_orient_matrix_UB_21      -0.0410108000
_diffrn_orient_matrix_UB_22      0.0300176000
_diffrn_orient_matrix_UB_23      -0.0628956000
_diffrn_orient_matrix_UB_31      -0.1241331000
_diffrn_orient_matrix_UB_32      -0.0243865000
_diffrn_orient_matrix_UB_33      0.0123732000
_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  0.0911
_diffrn_reflns_av_unetI/netI     0.1035
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       29
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            30897
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        66.599
_diffrn_reflns_theta_max         66.599
_diffrn_reflns_theta_min         3.678
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.903
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.49321
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.33c (Rigaku Oxford Diffraction, 2017)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light red'
_exptl_crystal_density_diffrn    1.282
_exptl_crystal_description       block
_exptl_crystal_F_000             1200
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.849
_refine_diff_density_min         -0.796
_refine_diff_density_rms         0.095
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.062
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     725
_refine_ls_number_reflns         10237
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.062
_refine_ls_R_factor_all          0.1254
_refine_ls_R_factor_gt           0.0954
_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^)+(0.1607P)^2^+2.8007P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2811
_refine_ls_wR_factor_ref         0.3041
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6484
_reflns_number_total             10237
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc06494a2.cif
_cod_data_source_block           06-0304
_cod_depositor_comments
'Adding full bibliography for 1573937--1573938.cif.'
_cod_database_code               1573938
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H O N S'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C15(H15A,H15B), C16(H16A,H16B), C31(H31A,H31B), C32(H32A,
 H32B), C33(H33A,H33B), C72(H72A,H72B), C73(H73A,H73B), C74(H74A,H74B),
 C77(H77A,H77B), C78(H78A,H78B), C79(H79A,H79B)
2.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C11(H11), C20(H20),
 C22(H22), C23(H23), C26(H26), C27(H27), C28(H28), C29(H29), C30(H30), C47(H47),
  C49(H49), C50(H50), C54(H54), C55(H55), C56(H56), C57(H57), C58(H58),
 C59(H59), C62(H62), C63(H63), C66(H66), C67(H67), C68(H68), C69(H69), C70(H70)
2.c Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C34(H34A,H34B,H34C), C75(H75A,H75B,H75C), C80(H80A,H80B,
 H80C)
;
_shelx_res_checksum              62287
_shelx_hkl_checksum              49638
_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 3.911
_oxdiff_exptl_absorpt_empirical_full_min 0.514