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_1570291
_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             2023-04-06
_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                 108.890(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.21813(19)
_cell_length_b                   19.4553(3)
_cell_length_c                   8.39007(17)
_cell_measurement_reflns_used    5424
_cell_measurement_temperature    100.00(13)
_cell_measurement_theta_max      68.0390
_cell_measurement_theta_min      4.5270
_cell_volume                     1423.65(5)
_computing_cell_refinement       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.84a (Rigaku OD, 2020)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(13)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix3000
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.986
_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    -34.00  28.00   0.50    1.20    --  -41.33  29.00  57.00  124
  2  \w    -24.00  35.00   0.50    1.20    --  -41.33  11.00  90.00  118
  3  \w     29.00 110.00   0.50    1.20    --   41.33  29.00  57.00  162
  4  \w     84.00 166.00   0.50    4.79    --   96.67  29.00  57.00  164
  5  \w     90.00 124.00   0.50    4.79    --   96.67 145.00 -90.00   68
  6  \w    135.00 163.00   0.50    4.79    --   96.67 145.00 -90.00   56
  7  \w     90.00 123.00   0.50    4.79    --   96.67 145.00 -60.00   66
  8  \w     80.00 160.00   0.50    4.79    --   96.67  42.00-120.00  160
  9  \w     39.00  64.00   0.50    4.79    --   96.67 -68.00 120.00   50
 10  \w     41.00  82.00   0.50    4.79    --   96.67 -68.00 150.00   82
 11  \w     37.00  97.00   0.50    4.79    --   96.67-117.00 150.00  120
 12  \w     44.00 110.00   0.50    4.79    --   96.67-145.00  60.00  132
 13  \w     41.00  67.00   0.50    4.79    --   96.67 -59.00 -90.00   52
 14  \w     38.00  92.00   0.50    4.79    --   96.67 -77.00 -90.00  108
 15  \w     40.00  83.00   0.50    4.79    --   96.67 -68.00-180.00   86
 16  \w     30.00  55.00   0.50    4.79    --   96.67 -50.00 -90.00   50
 17  \w     30.00  55.00   0.50    4.79    --   96.67 -50.00 -60.00   50
 18  \w     29.00  54.00   0.50    4.79    --   96.67 -59.00 -60.00   50
 19  \w     30.00  56.00   0.50    4.79    --   96.67 -50.00 -30.00   52
 20  \w     36.00  68.00   0.50    4.79    --   96.67 -59.00   0.00   64
 21  \w     30.00  55.00   0.50    4.79    --   96.67 -50.00  30.00   50
 22  \w     30.00  55.00   0.50    4.79    --   96.67 -50.00  90.00   50
 23  \w    -25.00  48.00   0.50    1.20    --   41.33 -43.00  60.00  146
 24  \w    -25.00  48.00   0.50    1.20    --   41.33 -43.00  90.00  146
 25  \w    -27.00  34.00   0.50    1.20    --   41.33 -29.00-103.00  122
 26  \w     18.00  80.00   0.50    1.20    --   41.33-104.00-120.00  124
 27  \w     30.00  56.00   0.50    4.79    --   96.67 -50.00-120.00   52
 28  \w     31.00  57.00   0.50    4.79    --   96.67 -50.00-150.00   52
 29  \w     29.00  55.00   0.50    4.79    --   96.67 -59.00-150.00   52
 30  \w    -65.00  26.00   0.50    1.20    --  -41.33  65.00 120.00  182
 31  \w    -47.00 -15.00   0.50    4.79    --  -82.50  42.00   0.00   64
 32  \w    -47.00 -15.00   0.50    4.79    --  -82.50  42.00  60.00   64
 33  \w    -47.00 -15.00   0.50    4.79    --  -82.50  42.00  30.00   64
 34  \w    -47.00 -15.00   0.50    4.79    --  -82.50  42.00 -90.00   64
 35  \w    -47.00 -15.00   0.50    4.79    --  -82.50  42.00-120.00   64
 36  \w    -83.00 -14.00   0.50    4.79    --  -82.50  68.00-180.00  138
 37  \w   -110.00 -29.00   0.50    1.20    --  -41.33 -29.00-103.00  162
 38  \w   -151.00 -70.00   0.50    4.79    --  -82.50 -29.00-103.00  162
;
_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      -0.1655206000
_diffrn_orient_matrix_UB_12      0.0275048000
_diffrn_orient_matrix_UB_13      -0.0519043000
_diffrn_orient_matrix_UB_21      -0.0167777000
_diffrn_orient_matrix_UB_22      -0.0115901000
_diffrn_orient_matrix_UB_23      -0.1867882000
_diffrn_orient_matrix_UB_31      -0.0593533000
_diffrn_orient_matrix_UB_32      -0.0733362000
_diffrn_orient_matrix_UB_33      0.0101315000
_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  0.0334
_diffrn_reflns_av_unetI/netI     0.0344
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            9254
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.226
_diffrn_reflns_theta_min         4.545
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.834
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.79888
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.84a (Rigaku Oxford Diffraction, 2020)
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    1.378
_exptl_crystal_description       needle
_exptl_crystal_F_000             612
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.159
_refine_diff_density_min         -0.239
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.052
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     200
_refine_ls_number_reflns         2566
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0445
_refine_ls_R_factor_gt           0.0375
_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^)+(0.0563P)^2^+0.2398P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0984
_refine_ls_wR_factor_ref         0.1028
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2164
_reflns_number_total             2566
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc03267a4.cif
_cod_data_source_block           kjk-etcetoh-needle
_cod_depositor_comments
'Adding full bibliography for 1570291--1570296.cif.'
_cod_database_code               1570291
_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   0.680
_reflns_odcompleteness_completeness 99.85
_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:
 C21(H21A,H21B)
2.b Aromatic/amide H refined with riding coordinates:
 C11(H11), C14(H14), C17(H17), C20(H20), C18(H18), C13(H13), C12(H12), C19(H19)
2.c Idealised Me refined as rotating group:
 C22(H22A,H22B,H22C)
;
_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 1.349
_oxdiff_exptl_absorpt_empirical_full_min 0.722