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_1570292
_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         'C8 F4 N2, C20 H25 N'
_chemical_formula_sum            'C28 H25 F4 N3'
_chemical_formula_weight         479.51
_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             2023-04-07
_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                70.393(4)
_cell_angle_beta                 86.036(4)
_cell_angle_gamma                79.883(4)
_cell_formula_units_Z            2
_cell_length_a                   6.7353(3)
_cell_length_b                   11.3696(5)
_cell_length_c                   16.8733(8)
_cell_measurement_reflns_used    4354
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      67.7320
_cell_measurement_theta_min      2.7710
_cell_volume                     1198.20(10)
_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_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.977
_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    -23.00  29.00   0.50    0.35    --  -41.33  21.00 -30.00  104
  2  \w    -21.00  19.00   0.50    0.35    --  -41.33  21.00  30.00   80
  3  \w     -9.00  29.00   0.50    0.35    --  -41.33  11.00 120.00   76
  4  \w    -24.00  32.00   0.50    0.35    --  -41.33  11.00  90.00  112
  5  \w    -26.00   3.00   0.50    0.35    --  -41.33  21.00   0.00   58
  6  \w    -47.00 -22.00   0.50    1.42    --  -82.50  42.00 -90.00   50
  7  \w    -27.00  26.00   0.50    0.35    --  -41.33  21.00-150.00  106
  8  \w    -45.00 -15.00   0.50    1.42    --  -82.50  42.00-180.00   60
  9  \w    -68.00 -27.00   0.50    0.35    --  -41.33 128.00-164.00   82
 10  \w    -45.00 -17.00   0.50    1.42    --  -82.50  42.00  30.00   56
 11  \w    -45.00 -16.00   0.50    1.42    --  -82.50  42.00  90.00   58
 12  \w    -57.00 -21.00   0.50    1.42    --  -82.50  50.00  60.00   72
 13  \w    -87.00 -40.00   0.50    0.35    --  -41.33 142.00   6.00   94
 14  \w    -84.00 -31.00   0.50    1.42    --  -82.50 117.00 120.00  106
 15  \w    -17.00  14.00   0.50    0.35    --   41.33 -43.00-120.00   62
 16  \w     23.00  48.00   0.50    0.35    --   41.33 -43.00-120.00   50
 17  \w     83.00 163.00   0.50    1.42    --   96.67  33.00 -30.00  160
 18  \w    107.00 140.00   0.50    1.42    --   96.67  96.00-120.00   66
 19  \w    130.00 163.00   0.50    1.42    --   96.67  96.00-180.00   66
 20  \w    134.00 162.00   0.50    1.42    --   96.67 145.00-120.00   56
 21  \w    111.00 164.00   0.50    1.42    --   96.67 117.00 -30.00  106
 22  \w     99.00 129.00   0.50    1.42    --   96.67 117.00-120.00   60
 23  \w     87.00 113.00   0.50    1.42    --   96.67 145.00-120.00   52
 24  \w     95.00 123.00   0.50    1.42    --   96.67 142.00   6.00   56
 25  \w     84.00 164.00   0.50    1.42    --   96.67  59.00  60.00  160
 26  \w    101.00 156.00   0.50    1.42    --   96.67  33.00  30.00  110
 27  \w     90.00 163.00   0.50    1.42    --   96.67  50.00   0.00  146
 28  \w     80.00 105.00   0.50    0.35    --   41.33  54.00-150.00   50
 29  \w     83.00 135.00   0.50    1.42    --   96.67  33.00-180.00  104
 30  \w     72.00 101.00   0.50    1.42    --   96.67 -77.00 -30.00   58
 31  \w     84.00 109.00   0.50    1.42    --   96.67-117.00  30.00   50
 32  \w     84.00 109.00   0.50    1.42    --   96.67-142.00 -49.00   50
 33  \w     83.00 108.00   0.50    1.42    --   96.67-117.00-150.00   50
 34  \w     72.00  98.00   0.50    0.35    --   41.33-142.00 -49.00   52
 35  \w     46.00  81.00   0.50    1.42    --   96.67 -68.00 -90.00   70
 36  \w     37.00  68.00   0.50    1.42    --   96.67 -77.00 -30.00   62
 37  \w     34.00 108.00   0.50    1.42    --   96.67-117.00 -90.00  148
 38  \w     35.00  82.00   0.50    1.42    --   96.67 -68.00   0.00   94
 39  \w     30.00  55.00   0.50    1.42    --   96.67 -50.00   0.00   50
 40  \w     31.00  57.00   0.50    1.42    --   96.67 -50.00  60.00   52
 41  \w     32.00  57.00   0.50    1.42    --   96.67 -50.00  90.00   50
 42  \w     53.00  92.00   0.50    1.42    --   96.67 -77.00 120.00   78
 43  \w     71.00  97.00   0.50    1.42    --   96.67-128.00 121.00   52
 44  \w     39.00  64.00   0.50    0.35    --   41.33-128.00 121.00   50
 45  \w     35.00  67.00   0.50    1.42    --   96.67 -59.00 150.00   64
 46  \w     30.00  55.00   0.50    1.42    --   96.67 -50.00 150.00   50
 47  \w     31.00  56.00   0.50    1.42    --   96.67 -50.00 120.00   50
 48  \w     29.00  67.00   0.50    1.42    --   96.67 -59.00  60.00   76
 49  \w     32.00  58.00   0.50    1.42    --   96.67-117.00  30.00   52
 50  \w     30.00  55.00   0.50    1.42    --   96.67 -50.00 -60.00   50
 51  \w     28.00 114.00   0.50    1.42    --   96.67 -87.00 -90.00  172
 52  \w     32.00  57.00   0.50    1.42    --   96.67 -50.00-120.00   50
 53  \w     31.00  56.00   0.50    1.42    --   96.67 -50.00 -90.00   50
 54  \w     30.00  55.00   0.50    1.42    --   96.67 -50.00-180.00   50
 55  \w     22.00  48.00   0.50    0.35    --   41.33  54.00-150.00   52
 56  \w    -33.00  -8.00   0.50    0.35    --   41.33 -11.00 -30.00   50
 57  \w     73.00  99.00   0.50    0.35    --   41.33  77.00 150.00   52
 58  \w     37.00  62.00   0.50    0.35    --   41.33  77.00 150.00   50
 59  \w    -97.00 -71.00   0.50    0.35    --  -41.33-142.00 -49.00   52
 60  \w   -111.00 -85.00   0.50    1.42    --  -82.50-142.00 -49.00   52
 61  \w   -107.00 -82.00   0.50    1.42    --  -82.50-128.00 121.00   50
 62  \w   -151.00 -74.00   0.50    1.42    --  -82.50  -8.00 120.00  154
 63  \w    -76.00 -51.00   0.50    1.42    --  -82.50 128.00-164.00   50
;
_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      -0.0121359000
_diffrn_orient_matrix_UB_12      0.0064255000
_diffrn_orient_matrix_UB_13      0.0899902000
_diffrn_orient_matrix_UB_21      -0.0527270000
_diffrn_orient_matrix_UB_22      0.1453075000
_diffrn_orient_matrix_UB_23      -0.0356812000
_diffrn_orient_matrix_UB_31      -0.2259610000
_diffrn_orient_matrix_UB_32      -0.0099299000
_diffrn_orient_matrix_UB_33      0.0045920000
_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  0.0420
_diffrn_reflns_av_unetI/netI     0.0528
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       5
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            10240
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.214
_diffrn_reflns_theta_min         2.780
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.842
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.83677
_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    1.329
_exptl_crystal_description       needle
_exptl_crystal_F_000             500
_exptl_crystal_size_max          0.7
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.280
_refine_diff_density_min         -0.426
_refine_diff_density_rms         0.065
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     322
_refine_ls_number_reflns         4280
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0571
_refine_ls_R_factor_gt           0.0493
_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^)+(0.0906P)^2^+0.1254P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1331
_refine_ls_wR_factor_ref         0.1413
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3567
_reflns_number_total             4280
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc03267a4.cif
_cod_data_source_block           kjkj_dtdc_1
_cod_depositor_comments
'Adding full bibliography for 1570291--1570296.cif.'
_cod_database_code               1570292
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N F'
_chemical_oxdiff_usercomment     @100K
_shelx_estimated_absorpt_t_max   0.921
_shelx_estimated_absorpt_t_min   0.590
_reflns_odcompleteness_completeness 99.01
_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 N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 N005(H005), C008(H008), C009(H009), C00B(H00B), C00J(H00J), C00L(H00L),
 C00M(H00M)
2.b Idealised Me refined as rotating group:
 C00T(H00A,H00C,H00D), C00U(H00E,H00F,H00G), C00W(H00H,H00I,H00K), C00X(H00N,
 H00O,H00P), C00Y(H00Q,H00R,H00S), C00Z(H00T,H00U,H00V)
;
_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 1.576
_oxdiff_exptl_absorpt_empirical_full_min 0.656