Deep-Blue Thermally Activated Delayed Fluorescence from a CF3-substituted Carbene-Metal-Amide Complex
Brannan, Alexander C.; Phuoc, Nguyen Le; Linnolahti, Mikko; Romanov, Alexander S.; Physical Chemistry Chemical Physics  (2025) –; doi:10.1039/D5CP00824G

data_7250547
_publ_section_title
;
 Deep-Blue Thermally Activated Delayed Fluorescence from a CF3-substituted
 Carbene-Metal-Amide Complex
;
_journal_name_full               'Physical Chemistry Chemical Physics'
_journal_paper_doi               10.1039/D5CP00824G
_journal_year                    2025
_chemical_formula_moiety         'C38 H44 Au F3 N4'
_chemical_formula_sum            'C38 H44 Au F3 N4'
_chemical_formula_weight         810.74
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-02-28
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-03-01 deposited with the CCDC.	2025-06-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.966(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.1448(3)
_cell_length_b                   15.7992(4)
_cell_length_c                   22.5860(6)
_cell_measurement_reflns_used    8250
_cell_measurement_temperature    99.97(18)
_cell_measurement_theta_max      74.9270
_cell_measurement_theta_min      3.4150
_cell_volume                     3593.36(17)
_computing_cell_refinement       'CrysAlisPro 1.171.42.53a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.53a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.53a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (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      99.97(18)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.965
_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    -34.00 117.00   0.50    0.50    --   43.53  20.00  30.00  302
  2  \w    -42.00  54.00   0.50    0.50    --   46.07  30.00 120.00  192
  3  \w     70.00 130.00   0.50    0.50    --   46.07  30.00 120.00  120
  4  \w     75.00 101.00   0.50    1.46    --  108.20  50.00-150.00   52
  5  \w     19.00 198.00   0.50    1.46    --  108.20  20.00 -60.00  358
  6  \w     20.00  78.00   0.50    1.46    --  108.20  50.00  90.00  116
  7  \w    107.00 198.00   0.50    1.46    --  108.20  30.00  90.00  182
  8  \w    100.00 198.00   0.50    1.46    --  108.20  50.00  90.00  196
  9  \w    102.00 129.00   0.50    1.46    --  108.20  50.00-150.00   54
 10  \w     21.00  92.00   0.50    1.46    --  108.20  10.00  90.00  142
 11  \w    143.00 197.00   0.50    1.46    --  108.20  10.00  90.00  108
 12  \w     29.00  57.00   0.50    1.46    --  108.20  50.00-150.00   56
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC11 (RINC): quarter-chi single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1330543000
_diffrn_orient_matrix_UB_12      -0.0473161000
_diffrn_orient_matrix_UB_13      0.0006621000
_diffrn_orient_matrix_UB_21      0.0011997000
_diffrn_orient_matrix_UB_22      -0.0177389000
_diffrn_orient_matrix_UB_23      0.0671813000
_diffrn_orient_matrix_UB_31      -0.0753640000
_diffrn_orient_matrix_UB_32      -0.0833586000
_diffrn_orient_matrix_UB_33      -0.0146616000
_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  0.0363
_diffrn_reflns_av_unetI/netI     0.0423
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.965
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            20361
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.965
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.087
_diffrn_reflns_theta_min         3.422
_diffrn_source                   'Rotating-anode X-ray tube (dual wavelength)'
_diffrn_source_type              'Rigaku (Cu) X-ray DW Source'
_exptl_absorpt_coefficient_mu    8.074
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.76282
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.53a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.499
_exptl_crystal_description       block
_exptl_crystal_F_000             1624
_exptl_crystal_preparation       Luminescent
_exptl_crystal_size_max          0.36
_exptl_crystal_size_mid          0.33
_exptl_crystal_size_min          0.28
_refine_diff_density_max         4.632
_refine_diff_density_min         -3.847
_refine_diff_density_rms         0.161
_refine_ls_extinction_coef       0.00005(2)
_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   1.140
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     424
_refine_ls_number_reflns         7256
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.140
_refine_ls_R_factor_all          0.0782
_refine_ls_R_factor_gt           0.0731
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+52.7763P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1528
_refine_ls_wR_factor_ref         0.1553
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6640
_reflns_number_total             7256
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cp00824g2.cif
_cod_data_source_block           lar14
_cod_original_cell_volume        3593.36(16)
_cod_database_code               7250547
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C20H20N3Au1
_shelx_estimated_absorpt_t_max   0.211
_shelx_estimated_absorpt_t_min   0.159
_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 Ternary CH refined with riding coordinates:
 C22(H22), C3(H3), C19(H19), C10(H10)
2.b Secondary CH2 refined with riding coordinates:
 C4(H4A,H4B), C6(H6A,H6B), C7(H7A,H7B)
2.c Aromatic/amide H refined with riding coordinates:
 C26(H26), C16(H16), C15(H15), C33(H33), C29(H29), C27(H27), C36(H36),
 C28(H28), C17(H17), C35(H35)
2.d Idealised Me refined as rotating group:
 C8(H8A,H8B,H8C), C9(H9A,H9B,H9C), C21(H21A,H21B,H21C), C24(H24A,H24B,H24C),
 C23(H23A,H23B,H23C), C12(H12A,H12B,H12C), C20(H20A,H20B,H20C), C11(H11A,H11B,
 H11C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_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 1.429
_oxdiff_exptl_absorpt_empirical_full_min 0.807