Thermally activated delayed fluorescence in a mechanically soft charge-transfer complex: role of the locally excited state.
Kalita, Kalyan Jyoti; Mondal, Saikat; Reddy, C. Malla; Vijayaraghavan, Ratheesh K.; Chemical science 14 (2023) 13870–13878; doi:10.1039/d3sc03267a

data_1570296
_publ_section_title
;
 Thermally activated delayed fluorescence in a mechanically soft
 charge-transfer complex: role of the locally excited state.
;
_journal_issue                   47
_journal_name_full               'Chemical science'
_journal_page_first              13870
_journal_page_last               13878
_journal_paper_doi               10.1039/d3sc03267a
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         'C4 F2 N, C14 H13 N'
_chemical_formula_sum            'C18 H13 F2 N2'
_chemical_formula_weight         295.30
_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             2023-04-11
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-05-04 deposited with the CCDC.	2023-11-06 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 107.396(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.2342(3)
_cell_length_b                   19.7739(4)
_cell_length_c                   8.5738(3)
_cell_measurement_reflns_used    14912
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      68.0490
_cell_measurement_theta_min      2.1760
_cell_volume                     1493.94(8)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_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    'SHELXT 2014/4 (Sheldrick, 2014)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.994
_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    -79.00   1.00   0.50    0.20    --  -40.27 108.00   8.00  160
  2  \w     21.00  79.00   0.50    0.20    --   40.27-108.00 -89.00  116
  3  \w   -150.00 -82.00   0.50    0.50    --  -82.50-108.00 -89.00  136
  4  \w    -83.00 -15.00   0.50    0.50    --  -82.50 108.00   8.00  136
  5  \w    103.00 164.00   0.50    0.50    --   96.35 108.00   8.00  122
  6  \w     29.00 108.00   0.50    0.50    --   96.35-108.00 -89.00  158
  7  \w   -110.00 -26.00   0.50    0.20    --  -40.27 -25.00   0.00  168
  8  \w   -108.00 -17.00   0.50    0.20    --  -40.27 -64.00-150.00  182
  9  \w     41.00  99.00   0.50    0.20    --   40.27-138.00-150.00  116
 10  \w    -35.00  24.00   0.50    0.20    --   40.27 -12.00 -90.00  118
 11  \w    -35.00  24.00   0.50    0.20    --   40.27 -12.00-150.00  118
 12  \w    -26.00  57.00   0.50    0.20    --   40.27 -50.00 -90.00  166
 13  \w    -47.00 -15.00   0.50    0.50    --  -82.50  42.00-150.00   64
 14  \w    -47.00 -15.00   0.50    0.50    --  -82.50  42.00 150.00   64
 15  \w   -156.00 -83.00   0.50    0.50    --  -82.50 -96.00  30.00  146
 16  \w    -68.00 -14.00   0.50    0.50    --  -82.50  59.00 -60.00  108
 17  \w     99.00 160.00   0.50    0.50    --   96.35 117.00-120.00  122
 18  \w     30.00  57.00   0.50    0.50    --   96.35 -50.00 -30.00   54
 19  \w     70.00 165.00   0.50    0.50    --   96.35  77.00   0.00  190
 20  \w     26.00 127.00   0.50    0.50    --   96.35 -87.00 -90.00  202
 21  \w    105.00 170.00   0.50    0.50    --   96.35  96.00 -30.00  130
 22  \w     30.00  57.00   0.50    0.50    --   96.35 -50.00  90.00   54
 23  \w     30.00  57.00   0.50    0.50    --   96.35 -50.00 -60.00   54
 24  \w     28.00  68.00   0.50    0.50    --   96.35 -59.00 -60.00   80
 25  \w     30.00  57.00   0.50    0.50    --   96.35 -50.00  60.00   54
 26  \w    105.00 170.00   0.50    0.50    --   96.35  96.00 -90.00  130
 27  \w     28.00  68.00   0.50    0.50    --   96.35 -59.00 120.00   80
 28  \w     30.00  57.00   0.50    0.50    --   96.35 -50.00 -90.00   54
 29  \w     44.00 127.00   0.50    0.50    --   96.35-145.00 120.00  166
 30  \w     99.00 160.00   0.50    0.50    --   96.35 117.00 -60.00  122
 31  \w     29.00  83.00   0.50    0.50    --   96.35 -68.00   0.00  108
 32  \w     28.00 105.00   0.50    0.50    --   96.35 -77.00 -90.00  154
 33  \w     99.00 160.00   0.50    0.50    --   96.35 117.00 -30.00  122
 34  \w   -109.00 -13.00   0.50    0.20    --  -40.27 -77.00 -90.00  192
 35  \w   -109.00 -13.00   0.50    0.20    --  -40.27 -77.00   0.00  192
 36  \w    -24.00  35.00   0.50    0.20    --  -40.27  12.00 150.00  118
 37  \w   -109.00 -13.00   0.50    0.20    --  -40.27 -77.00 120.00  192
 38  \w   -109.00 -13.00   0.50    0.20    --  -40.27 -77.00-180.00  192
 39  \w   -109.00 -13.00   0.50    0.20    --  -40.27 -77.00  60.00  192
 40  \w   -106.00 -25.00   0.50    0.20    --  -40.27 -38.00 -90.00  162
 41  \w   -109.00 -13.00   0.50    0.20    --  -40.27 -77.00 150.00  192
 42  \w   -109.00 -13.00   0.50    0.20    --  -40.27 -77.00 -30.00  192
 43  \w    -30.00  31.00   0.50    0.20    --   40.27 -25.00 -30.00  122
 44  \w   -151.00 -55.00   0.50    0.50    --  -82.50 -77.00-180.00  192
 45  \w   -151.00 -55.00   0.50    0.50    --  -82.50 -77.00 150.00  192
 46  \w   -151.00 -55.00   0.50    0.50    --  -82.50 -77.00-150.00  192
 47  \w   -151.00 -55.00   0.50    0.50    --  -82.50 -77.00 -60.00  192
 48  \w   -151.00 -55.00   0.50    0.50    --  -82.50 -77.00 120.00  192
 49  \w   -151.00 -55.00   0.50    0.50    --  -82.50 -77.00-120.00  192
 50  \w   -151.00 -55.00   0.50    0.50    --  -82.50 -77.00 -90.00  192
 51  \w   -151.00 -55.00   0.50    0.50    --  -82.50 -77.00 -30.00  192
 52  \w   -151.00 -55.00   0.50    0.50    --  -82.50 -77.00  60.00  192
 53  \w     77.00 163.00   0.50    0.50    --   96.35  50.00 -60.00  172
 54  \w     77.00 163.00   0.50    0.50    --   96.35  50.00-180.00  172
 55  \w     83.00 164.00   0.50    0.50    --   96.35  33.00-120.00  162
 56  \w     33.00 110.00   0.50    0.50    --   96.35-117.00-150.00  154
 57  \w     83.00 164.00   0.50    0.50    --   96.35  33.00  90.00  162
 58  \w     72.00 164.00   0.50    0.50    --   96.35  68.00  90.00  184
 59  \w     81.00 167.00   0.50    0.50    --   96.35  25.00 150.00  172
 60  \w     72.00 164.00   0.50    0.50    --   96.35  68.00 -30.00  184
 61  \w     70.00 165.00   0.50    0.50    --   96.35  77.00-120.00  190
 62  \w     70.00 165.00   0.50    0.50    --   96.35  77.00  30.00  190
 63  \w     23.00 106.00   0.50    0.50    --   96.35 -96.00  90.00  166
 64  \w    -96.00 -19.00   0.50    0.20    --  -40.27 138.00 -30.00  154
 65  \w   -109.00 -13.00   0.50    0.20    --  -40.27 -77.00 -60.00  192
 66  \w   -109.00 -13.00   0.50    0.20    --  -40.27 -77.00  30.00  192
 67  \w   -109.00 -13.00   0.50    0.20    --  -40.27 -77.00-150.00  192
 68  \w   -109.00 -13.00   0.50    0.20    --  -40.27 -77.00  90.00  192
 69  \w    -30.00  31.00   0.50    0.20    --   40.27 -25.00 150.00  122
 70  \w     13.00 109.00   0.50    0.20    --   40.27  77.00 -60.00  192
 71  \w     13.00 109.00   0.50    0.20    --   40.27  77.00  90.00  192
 72  \w     18.00  78.00   0.50    0.20    --   40.27-104.00 150.00  120
 73  \w     13.00 109.00   0.50    0.20    --   40.27  77.00 150.00  192
 74  \w   -151.00 -55.00   0.50    0.50    --  -82.50 -77.00  30.00  192
 75  \w   -151.00 -55.00   0.50    0.50    --  -82.50 -77.00  90.00  192
 76  \w   -151.00 -55.00   0.50    0.50    --  -82.50 -77.00   0.00  192
 77  \w     70.00 165.00   0.50    0.50    --   96.35  77.00-180.00  190
 78  \w     72.00 164.00   0.50    0.50    --   96.35  68.00 120.00  184
 79  \w     72.00 164.00   0.50    0.50    --   96.35  68.00 -90.00  184
 80  \w     70.00 165.00   0.50    0.50    --   96.35  77.00-150.00  190
 81  \w     70.00 165.00   0.50    0.50    --   96.35  77.00  60.00  190
 82  \w     70.00 165.00   0.50    0.50    --   96.35  77.00 -60.00  190
 83  \w     70.00 165.00   0.50    0.50    --   96.35  77.00 150.00  190
 84  \w     70.00 165.00   0.50    0.50    --   96.35  77.00 120.00  190
 85  \w     80.00 164.00   0.50    0.50    --   96.35  42.00  30.00  168
 86  \w     26.00 127.00   0.50    0.50    --   96.35 -87.00 120.00  202
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix3000'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1188041000
_diffrn_orient_matrix_UB_12      0.0570748000
_diffrn_orient_matrix_UB_13      0.0429289000
_diffrn_orient_matrix_UB_21      0.1174800000
_diffrn_orient_matrix_UB_22      -0.0496547000
_diffrn_orient_matrix_UB_23      0.1057145000
_diffrn_orient_matrix_UB_31      0.0513332000
_diffrn_orient_matrix_UB_32      -0.0186166000
_diffrn_orient_matrix_UB_33      -0.1498154000
_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  0.0389
_diffrn_reflns_av_unetI/netI     0.0128
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            36060
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.251
_diffrn_reflns_theta_min         4.472
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.795
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.50115
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellowish yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   yellowish
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.313
_exptl_crystal_description       needle
_exptl_crystal_F_000             612
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.143
_refine_diff_density_min         -0.093
_refine_diff_density_rms         0.027
_refine_ls_extinction_coef       0.0028(4)
_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     201
_refine_ls_number_reflns         2718
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.076
_refine_ls_R_factor_all          0.0426
_refine_ls_R_factor_gt           0.0379
_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^)+(0.0563P)^2^+0.1530P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1091
_refine_ls_wR_factor_ref         0.1132
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2359
_reflns_number_total             2718
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc03267a4.cif
_cod_data_source_block           kjk-etc-tf1_test1
_cod_depositor_comments
'Adding full bibliography for 1570291--1570296.cif.'
_cod_database_code               1570296
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N F'
_shelx_estimated_absorpt_t_max   0.925
_shelx_estimated_absorpt_t_min   0.692
_reflns_odcompleteness_completeness 100.00
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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:
 C00L(H00A,H00C)
2.b Aromatic/amide H refined with riding coordinates:
 C009(H009), C00B(H00B), C00E(H00E), C00F(H00F), C00G(H00G), C00I(H00I),
 C00J(H00J), C00K(H00K)
2.c Idealised Me refined as rotating group:
 C00M(H00D,H00H,H00L)
;
_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 1.595
_oxdiff_exptl_absorpt_empirical_full_min 0.609