Achieving dual emission of thermally activated delayed fluorescence and ultralong room-temperature phosphorescence by controlling excited state dynamics through metal coordination
Cai, Xian-Bao; Liang, Dong; Zhang, Deng-Chao; Jia, Ji-Hui; Wu, Xiao-Yuan; Lu, Can-Zhong; Chemical Science 16 (2025) 9802–9808; doi:10.1039/D5SC00555H

data_1574484
_publ_section_title
;
 Achieving dual emission of thermally activated delayed fluorescence and
 ultralong room-temperature phosphorescence by controlling excited state
 dynamics through metal coordination
;
_journal_issue                   22
_journal_name_full               'Chemical Science'
_journal_page_first              9802
_journal_page_last               9808
_journal_paper_doi               10.1039/D5SC00555H
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         '2(C48 H34 N4), 2(C7 H7.294 O0.583), 4(H2 O)'
_chemical_formula_sum            'C110 H92 N8 O4.5'
_chemical_formula_weight         1597.91
_chemical_name_systematic        Phen-Tpa
_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   mixed
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2m1v0k
_audit_creation_date             2024-12-08
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-01-06 deposited with the CCDC.	2025-04-21 downloaded from the CCDC.
;
_cell_angle_alpha                89.8470(10)
_cell_angle_beta                 85.1040(10)
_cell_angle_gamma                75.2930(10)
_cell_formula_units_Z            1
_cell_length_a                   9.74650(10)
_cell_length_b                   10.17140(10)
_cell_length_c                   21.3460(2)
_cell_measurement_reflns_used    28194
_cell_measurement_temperature    101(2)
_cell_measurement_theta_max      56.3090
_cell_measurement_theta_min      1.8940
_cell_volume                     2038.95(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46c (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46c (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46c (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2014/7 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      101(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.975
_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     20.00 111.00   0.50    0.05    --   68.60-125.00-180.00  182
  2  \w     20.00 111.00   0.50    0.05    --   68.60-125.00-180.00  182
  3  \w     20.00 111.00   0.50    0.05    --   68.60-125.00-150.00  182
  4  \w     -5.00 101.00   0.50    0.05    --   68.60 -85.00-103.00  212
  5  \w     20.00 111.00   0.50    0.05    --   68.60-125.00  30.00  182
  6  \w     -5.00  92.00   0.50    0.05    --   68.60 -57.00   0.00  194
  7  \w     -5.00  92.00   0.50    0.05    --   68.60 -57.00   0.00  194
  8  \w     -5.00  92.00   0.50    0.05    --   68.60 -57.00  90.00  194
  9  \w     82.00 141.00   0.50    0.05    --   68.60  85.00  15.00  118
 10  \w     79.00 140.00   0.50    0.05    --   68.60 125.00  90.00  122
 11  \w    -73.00  23.00   0.50    0.05    --   -0.39 -57.00  90.00  192
 12  \w   -116.00 -79.00   0.50    0.05    --  -69.38-125.00 150.00   74
 13  \w   -141.00 -79.00   0.50    0.05    --  -69.38-125.00  60.00  124
 14  \w   -142.00 -91.00   0.50    0.05    --  -69.38 -99.00 -30.00  102
 15  \w    -73.00  23.00   0.50    0.05    --   -0.39 -57.00-120.00  192
 16  \w     -8.00  38.00   0.50    0.05    --   -0.39 -99.00-180.00   92
 17  \w    -73.00  23.00   0.50    0.05    --   -0.39 -57.00-120.00  192
 18  \w    -38.00  32.00   0.50    0.05    --   -0.39 -85.00-103.00  140
 19  \w   -142.00 -88.00   0.50    0.05    --  -69.38 -99.00   0.00  108
 20  \w   -142.00 -82.00   0.50    0.05    --  -69.38 -85.00-103.00  120
 21  \w   -128.00 -90.00   0.50    0.05    --  -69.38 -99.00-150.00   76
 22  \w   -131.00 -41.00   0.50    0.05    --  -69.38 -77.00-150.00  180
 23  \w   -143.00 -67.00   0.50    0.05    --  -69.38 -77.00 -90.00  152
 24  \w   -143.00 -67.00   0.50    0.05    --  -69.38 -77.00 -90.00  152
 25  \w    -20.00   5.00   0.50    0.05    --  -69.38  77.00-180.00   50
 26  \w    -33.00  39.00   0.50    0.05    --   -0.39  85.00  15.00  144
 27  \w    -75.00 -39.00   0.50    0.05    --  -69.38 125.00   0.00   72
 28  \w   -111.00 -78.00   0.50    0.05    --  -69.38 125.00   0.00   66
 29  \w   -102.00   5.00   0.50    0.05    --  -69.38  85.00  15.00  214
 30  \w    -73.00 -46.00   0.50    0.05    --  -69.38  77.00-180.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0917403000
_diffrn_orient_matrix_UB_12      -0.0442484000
_diffrn_orient_matrix_UB_13      0.0397095000
_diffrn_orient_matrix_UB_21      -0.1020548000
_diffrn_orient_matrix_UB_22      0.0419357000
_diffrn_orient_matrix_UB_23      -0.0391289000
_diffrn_orient_matrix_UB_31      0.0387907000
_diffrn_orient_matrix_UB_32      -0.1217377000
_diffrn_orient_matrix_UB_33      -0.0293007000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'micro-focus metaljet'
_diffrn_radiation_wavelength     1.3405
_diffrn_reflns_av_R_equivalents  0.0328
_diffrn_reflns_av_unetI/netI     0.0222
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            38753
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        53.543
_diffrn_reflns_theta_max         56.315
_diffrn_reflns_theta_min         1.806
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    0.400
_exptl_absorpt_correction_T_max  0.954
_exptl_absorpt_correction_T_min  0.869
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46c (Rigaku Oxford Diffraction, 2018)
Analytical numeric absorption correction using a multifaceted crystal
			model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear bluish green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   bluish
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.301
_exptl_crystal_description       block
_exptl_crystal_F_000             844
_exptl_crystal_preparation       none
_exptl_crystal_recrystallization_method none
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.265
_refine_diff_density_min         -0.253
_refine_diff_density_rms         0.041
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     587
_refine_ls_number_reflns         7974
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0408
_refine_ls_R_factor_gt           0.0376
_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^)+(0.0439P)^2^+0.8125P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0930
_refine_ls_wR_factor_ref         0.0957
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7286
_reflns_number_total             7974
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc00555h2.cif
_cod_data_source_block           abs2
_cod_depositor_comments
'Adding full bibliography for 1574484--1574485.cif.'
_cod_original_formula_sum        'C110 H92 N8 O4.50'
_cod_database_code               1574484
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C110 H92 N8 O4'
_shelx_estimated_absorpt_t_max   0.942
_shelx_estimated_absorpt_t_min   0.924
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All O(H) groups, All O(H,H) groups
2. Others
 Sof(O60)=Sof(H60)=FVAR(1)
3.a Free rotating group:
 O60(H60), O61(H61A,H61B), O62(H62A,H62B)
3.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C4(H4), C6(H6), C7(H7), C9(H9), C11(H11), C16(H16), C17(H17),
 C19(H19), C20(H20), C22(H22), C23(H23), C24(H24), C25(H25), C26(H26), C28(H28),
  C29(H29), C30(H30), C31(H31), C32(H32), C35(H35), C36(H36), C38(H38),
 C39(H39), C41(H41), C42(H42), C43(H43), C44(H44), C45(H45), C47(H47), C48(H48),
  C49(H49), C50(H50), C51(H51), C54(H54), C55(H55), C56(H56), C57(H57), C58(H58)
;
_shelx_res_checksum              22502
_olex2_exptl_crystal_mounting_method loop
_olex2_submission_original_sample_id Phen-Tpa
_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 1.582
_oxdiff_exptl_absorpt_empirical_full_min 0.477