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_1574485
_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         'C87 H66 Ag N4 O P2, B F4, C7 H8'
_chemical_formula_sum            'C94 H74 Ag B F4 N4 O P2'
_chemical_formula_weight         1532.19
_chemical_name_systematic        Ag+DTPA
_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_block_doi                 10.5517/ccdc.csd.cc2m1v1l
_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                77.0980(10)
_cell_angle_beta                 81.031(2)
_cell_angle_gamma                77.6880(10)
_cell_formula_units_Z            2
_cell_length_a                   12.9145(2)
_cell_length_b                   15.9498(2)
_cell_length_c                   19.2708(4)
_cell_measurement_reflns_used    34684
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      56.2600
_cell_measurement_theta_min      2.4850
_cell_volume                     3755.75(11)
_computing_cell_refinement       'CrysAlisPro 1.171.43.116a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.116a 64-bit (release 22-03-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.116a (Rigaku OD, 2024)'
_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      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.982
_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      7.00  87.00   0.50    0.16    --   68.67 -57.00  30.00  160
  2  \w      0.00  26.00   0.50    0.16    --   68.67 -77.00   0.00   52
  3  \w     29.00  98.00   0.50    0.16    --   68.67 -77.00   0.00  138
  4  \w     12.00  60.00   0.50    0.16    --   68.67 -38.00-180.00   96
  5  \w     47.00 143.00   0.50    0.16    --   68.67  57.00-120.00  192
  6  \w     89.00 114.00   0.50    0.16    --   68.67  94.00-114.00   50
  7  \w     47.00 137.00   0.50    0.16    --   68.67  77.00 -30.00  180
  8  \w    -26.00  29.00   0.50    0.05    --   -0.62  94.00-114.00  110
  9  \w   -110.00 -20.00   0.50    0.16    --  -69.92 125.00-120.00  180
 10  \w    -83.00 -19.00   0.50    0.16    --  -69.92  94.00-114.00  128
 11  \w   -109.00 -65.00   0.50    0.16    --  -69.92 125.00 -30.00   88
 12  \w    -79.00 -54.00   0.50    0.16    --  -69.92 125.00  30.00   50
 13  \w   -106.00 -27.00   0.50    0.16    --  -69.92 125.00 120.00  158
 14  \w    -93.00 -64.00   0.50    0.16    --  -69.92  57.00  30.00   58
 15  \w    -22.00  56.00   0.50    0.05    --   -0.62  57.00-150.00  156
 16  \w    -42.00   3.00   0.50    0.16    --  -69.92  57.00  30.00   90
 17  \w     54.00  95.00   0.50    0.16    --   68.67-125.00-180.00   82
 18  \w     -5.00  79.00   0.50    0.16    --   68.67 -94.00 134.00  168
 19  \w    -72.00  19.00   0.50    0.05    --   -0.62 -77.00  90.00  182
 20  \w   -126.00 -88.00   0.50    0.16    --  -69.92 -99.00  90.00   76
 21  \w   -129.00-104.00   0.50    0.16    --  -69.92-125.00 120.00   50
 22  \w   -114.00 -85.00   0.50    0.16    --  -69.92 -94.00 134.00   58
 23  \w   -141.00 -80.00   0.50    0.16    --  -69.92-125.00  30.00  122
 24  \w   -139.00 -96.00   0.50    0.16    --  -69.92 -99.00-180.00   86
 25  \w   -123.00 -92.00   0.50    0.16    --  -69.92 -99.00-120.00   62
 26  \w    -21.00   4.00   0.50    0.05    --   -0.62 -94.00 134.00   50
;
_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      -0.0096062000
_diffrn_orient_matrix_UB_12      0.0175430000
_diffrn_orient_matrix_UB_13      0.0657466000
_diffrn_orient_matrix_UB_21      -0.1011603000
_diffrn_orient_matrix_UB_22      -0.0122210000
_diffrn_orient_matrix_UB_23      0.0110288000
_diffrn_orient_matrix_UB_31      0.0329742000
_diffrn_orient_matrix_UB_32      -0.0850091000
_diffrn_orient_matrix_UB_33      0.0265540000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Ga K\a'
_diffrn_radiation_wavelength     1.3405
_diffrn_reflns_av_R_equivalents  0.0435
_diffrn_reflns_av_unetI/netI     0.0443
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            48504
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        53.543
_diffrn_reflns_theta_max         56.365
_diffrn_reflns_theta_min         2.058
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    2.053
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64723
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.116a (Rigaku Oxford Diffraction, 2024)
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    1.355
_exptl_crystal_description       block
_exptl_crystal_F_000             1584
_exptl_crystal_preparation       none
_exptl_crystal_recrystallization_method none
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.857
_refine_diff_density_min         -0.683
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     967
_refine_ls_number_reflns         14788
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0433
_refine_ls_R_factor_gt           0.0339
_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^)+(0.0396P)^2^+2.4400P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0824
_refine_ls_wR_factor_ref         0.0852
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13191
_reflns_number_total             14788
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc00555h2.cif
_cod_data_source_block           cxb_1_auto
_cod_depositor_comments
'Adding full bibliography for 1574484--1574485.cif.'
_cod_database_code               1574485
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         'C H N Cl'
_shelx_estimated_absorpt_t_max   0.821
_shelx_estimated_absorpt_t_min   0.578
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C12(H12), C84(H84), C14(H14), C76(H76), C10(H10), C1(H1), C85(H85), C83(H83),
 C9(H9), C38(H38), C72(H72), C74(H74), C39(H39), C36(H36), C71(H71), C23(H23),
 C7(H7), C75(H75), C2(H2), C40(H40), C21(H21), C33(H33), C15(H15), C68(H68),
 C64(H64), C22(H22), C24(H24), C18(H18), C48(H48), C32(H32), C17(H17), C47(H47),
  C54(H54), C44(H44), C35(H35), C69(H69), C20(H20), C41(H41), C66(H66),
 C42(H42), C50(H50), C62(H62), C65(H65), C70(H70), C26(H26), C60(H60), C57(H57),
  C30(H30), C52(H52), C53(H53), C56(H56), C45(H45), C63(H63), C46(H46),
 C51(H51), C92(H92), C29(H29), C58(H58), C59(H59), C28(H28), C93(H93), C89(H89),
  C90(H90), C27(H27), C91(H91)
2.b Idealised Me refined as rotating group:
 C86(H86a,H86b,H86c), C87(H87a,H87b,H87c), C94(H94a,H94b,H94c)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              99089
_shelx_fab_checksum              62262
_olex2_exptl_crystal_mounting_method loop
_olex2_submission_original_sample_id Ag-DTPA
_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 1.746
_oxdiff_exptl_absorpt_empirical_full_min 0.569