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_1570293
_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         'C14 H13 N, C12 H4 N4'
_chemical_formula_sum            'C26 H17 N5'
_chemical_formula_weight         399.45
_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             2023-04-11
_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                95.636(3)
_cell_angle_beta                 94.087(2)
_cell_angle_gamma                94.166(3)
_cell_formula_units_Z            2
_cell_length_a                   6.6187(2)
_cell_length_b                   9.1334(3)
_cell_length_c                   16.8821(5)
_cell_measurement_reflns_used    6815
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      67.9270
_cell_measurement_theta_min      2.6300
_cell_volume                     1009.76(5)
_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 0.998
_diffrn_measured_fraction_theta_max 0.988
_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    -76.00  24.00   0.50    0.40    --  -40.33  99.00  64.00  200
  2  \w     -2.00  76.00   0.50    0.40    --   40.33 -99.00 -41.00  156
  3  \w    -81.00  -9.00   0.50    2.10    --  -82.50  99.00  64.00  144
  4  \w   -156.00 -85.00   0.50    2.10    --  -82.50 -99.00 -41.00  142
  5  \w    107.00 170.00   0.50    2.10    --   96.67  99.00  64.00  126
  6  \w     24.00 106.00   0.50    2.10    --   96.67 -99.00 -41.00  164
  7  \w   -107.00 -21.00   0.50    0.40    --  -40.33 -50.00-180.00  172
  8  \w    -43.00  26.00   0.50    0.40    --  -40.33  38.00  30.00  138
  9  \w    -56.00  26.00   0.50    0.40    --  -40.33  50.00-180.00  164
 10  \w    -43.00  26.00   0.50    0.40    --  -40.33  38.00-180.00  138
 11  \w    -24.00  35.00   0.50    0.40    --  -40.33  12.00 -60.00  118
 12  \w    -24.00  35.00   0.50    0.40    --  -40.33  12.00 120.00  118
 13  \w    -24.00  35.00   0.50    0.40    --  -40.33  12.00 -30.00  118
 14  \w     41.00  99.00   0.50    0.40    --   40.33-138.00 -90.00  116
 15  \w    -30.00  31.00   0.50    0.40    --   40.33 -25.00 -30.00  122
 16  \w    -26.00  43.00   0.50    0.40    --   40.33 -38.00-150.00  138
 17  \w   -156.00 -58.00   0.50    2.10    --  -82.50 -17.00  60.00  196
 18  \w    -47.00 -15.00   0.50    2.10    --  -82.50  42.00  90.00   64
 19  \w   -151.00 -55.00   0.50    2.10    --  -82.50 -77.00   0.00  192
 20  \w   -149.00 -78.00   0.50    2.10    --  -82.50-117.00  60.00  142
 21  \w    -68.00 -14.00   0.50    2.10    --  -82.50  59.00 -30.00  108
 22  \w     29.00  83.00   0.50    2.10    --   96.67 -68.00-120.00  108
 23  \w     70.00 165.00   0.50    2.10    --   96.67  77.00 120.00  190
 24  \w     70.00 165.00   0.50    2.10    --   96.67  77.00 150.00  190
 25  \w     75.00 164.00   0.50    2.10    --   96.67  59.00  60.00  178
 26  \w     28.00 105.00   0.50    2.10    --   96.67 -77.00-180.00  154
 27  \w    105.00 170.00   0.50    2.10    --   96.67  96.00 -60.00  130
 28  \w    105.00 170.00   0.50    2.10    --   96.67  96.00  90.00  130
 29  \w     30.00  57.00   0.50    2.10    --   96.67 -50.00-180.00   54
 30  \w     30.00 109.00   0.50    2.10    --   96.67-117.00 -90.00  158
 31  \w     22.00 106.00   0.50    2.10    --   96.67 -96.00 150.00  168
 32  \w     99.00 164.00   0.50    2.10    --   96.67 117.00 -30.00  130
 33  \w     29.00  83.00   0.50    2.10    --   96.67 -68.00 -60.00  108
 34  \w     30.00  57.00   0.50    2.10    --   96.67 -50.00-120.00   54
 35  \w     22.00 106.00   0.50    2.10    --   96.67 -96.00-120.00  168
 36  \w     44.00 127.00   0.50    2.10    --   96.67-145.00-120.00  166
 37  \w     29.00  83.00   0.50    2.10    --   96.67 -68.00 -30.00  108
 38  \w     28.00 105.00   0.50    2.10    --   96.67 -77.00  60.00  154
 39  \w     73.00 165.00   0.50    2.10    --   96.67  68.00  30.00  184
 40  \w     71.00 170.00   0.50    2.10    --   96.67  17.00  30.00  198
 41  \w     83.00 164.00   0.50    2.10    --   96.67  33.00-150.00  162
 42  \w     30.00 109.00   0.50    2.10    --   96.67-117.00 120.00  158
 43  \w     29.00  83.00   0.50    2.10    --   96.67 -68.00   0.00  108
 44  \w     99.00 164.00   0.50    2.10    --   96.67 117.00-120.00  130
 45  \w   -106.00 -25.00   0.50    0.40    --  -40.33 -38.00  30.00  162
 46  \w   -108.00 -17.00   0.50    0.40    --  -40.33 -64.00   0.00  182
 47  \w   -109.00 -13.00   0.50    0.40    --  -40.33 -77.00 120.00  192
 48  \w   -109.00 -13.00   0.50    0.40    --  -40.33 -77.00 -90.00  192
 49  \w   -109.00 -13.00   0.50    0.40    --  -40.33 -77.00 -30.00  192
 50  \w     14.00 109.00   0.50    0.40    --   40.33  77.00-180.00  190
 51  \w     14.00 109.00   0.50    0.40    --   40.33  77.00-120.00  190
 52  \w     14.00 109.00   0.50    0.40    --   40.33  77.00 120.00  190
 53  \w     21.00 107.00   0.50    0.40    --   40.33  50.00 -30.00  172
;
_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      0.0452865000
_diffrn_orient_matrix_UB_12      -0.0566602000
_diffrn_orient_matrix_UB_13      -0.0853898000
_diffrn_orient_matrix_UB_21      0.0554667000
_diffrn_orient_matrix_UB_22      0.1597185000
_diffrn_orient_matrix_UB_23      -0.0175595000
_diffrn_orient_matrix_UB_31      0.2228888000
_diffrn_orient_matrix_UB_32      -0.0139053000
_diffrn_orient_matrix_UB_33      0.0293507000
_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  0.0731
_diffrn_reflns_av_unetI/netI     0.0499
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -7
_diffrn_reflns_limit_k_max       10
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            14382
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         68.548
_diffrn_reflns_theta_min         2.638
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.636
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.45470
_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 dark black'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.314
_exptl_crystal_description       needle
_exptl_crystal_F_000             416
_exptl_crystal_size_max          0.8
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.911
_refine_diff_density_min         -0.418
_refine_diff_density_rms         0.173
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     281
_refine_ls_number_reflns         3652
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0853
_refine_ls_R_factor_gt           0.0786
_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^)+(0.1754P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2065
_refine_ls_wR_factor_ref         0.2183
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3098
_reflns_number_total             3652
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc03267a4.cif
_cod_data_source_block           kjk_czc2_tcnq_1
_cod_depositor_comments
'Adding full bibliography for 1570291--1570296.cif.'
_cod_database_code               1570293
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C H N'
_chemical_oxdiff_usercomment     '100 K'
_shelx_estimated_absorpt_t_max   0.939
_shelx_estimated_absorpt_t_min   0.630
_reflns_odcompleteness_completeness 99.97
_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:
 C00U(H00A,H00B)
2.b Aromatic/amide H refined with riding coordinates:
 C00B(H00F), C00D(H00G), C00H(H00H), C00K(H00K), C00L(H00L), C00N(H00N),
 C00O(H00O), C00P(H00P), C00Q(H00Q), C00R(H00R), C00S(H00S), C00T(H00T)
2.c Idealised Me refined as rotating group:
 C00V(H00C,H00D,H00E)
;
_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 1.715
_oxdiff_exptl_absorpt_empirical_full_min 0.416