CO2-enhanced TADF of an ultra-stable Cu(i) cluster via guest–host π–π interaction
Zhang, Hong-Jin; Chen, Zong-Ren; Xu, Ji-Tong; Ye, Jia-Wen; Chen, Ling; Chen, Xiao-Ming; Chemical Science 16 (2025) 6872–6878; doi:10.1039/D4SC07949C

data_1574116
_publ_section_title
;
 CO2-enhanced TADF of an ultra-stable Cu(i) cluster via guest--host \p--\p
 interaction
;
_journal_issue                   16
_journal_name_full               'Chemical Science'
_journal_page_first              6872
_journal_page_last               6878
_journal_paper_doi               10.1039/D4SC07949C
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C72 H56 Cu2 I2 O2 P4, 2(C0.8 O1.562)'
_chemical_formula_sum            'C73.6 H56 Cu2 I2 O5.12 P4'
_chemical_formula_weight         1527.14
_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             2024-05-06
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2024-10-24 deposited with the CCDC.	2025-03-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 116.6880(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.30730(10)
_cell_length_b                   19.28920(10)
_cell_length_c                   14.7456(2)
_cell_measurement_reflns_used    29488
_cell_measurement_temperature    150.00(11)
_cell_measurement_theta_max      77.6910
_cell_measurement_theta_min      3.7150
_cell_volume                     3381.77(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.94a (Rigaku OD, 2023)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.00(11)
_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 1.000
_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    -81.00   2.00   0.50    2.00    --  -50.49 105.00 129.00  166
  2  \w     33.00  59.00   0.50    2.00    --   50.49-105.00  29.00   52
  3  \w   -135.00-109.00   0.50   15.00    --  -90.00-105.00  29.00   52
  4  \w    -61.00 -35.00   0.50   15.00    --  -90.00 105.00 129.00   52
  5  \w     77.00 107.00   0.50   15.00    --  108.07-105.00  29.00   60
  6  \w    105.00 158.00   0.50   15.00    --  108.07 105.00 129.00  106
  7  \w    -24.00  20.00   0.50    2.00    --  -50.49  19.00  30.00   88
  8  \w   -120.00 -31.00   0.50    2.00    --  -50.49 -77.00   0.00  178
  9  \w    -26.00  -1.00   0.50    2.00    --  -50.49  19.00  90.00   50
 10  \w    -14.00  23.00   0.50    2.00    --  -50.49  19.00-120.00   74
 11  \w   -119.00 -94.00   0.50    2.00    --  -50.49-125.00 150.00   50
 12  \w   -115.00 -89.00   0.50    2.00    --  -50.49-125.00 -30.00   52
 13  \w    -63.00  22.00   0.50    2.00    --  -50.49  57.00 120.00  170
 14  \w   -155.00 -88.00   0.50   15.00    --  -90.00 -19.00  30.00  134
 15  \w   -157.00 -87.00   0.50   15.00    --  -90.00 -99.00-180.00  140
 16  \w    -83.00 -22.00   0.50   15.00    --  -90.00 125.00 -30.00  122
 17  \w    -54.00 -25.00   0.50   15.00    --  -90.00  57.00  30.00   58
 18  \w   -113.00 -84.00   0.50   15.00    --  -90.00 -38.00  60.00   58
 19  \w    -65.00 -28.00   0.50   15.00    --  -90.00  57.00-150.00   74
 20  \w    -65.00 -21.00   0.50   15.00    --  -90.00 125.00 -60.00   88
 21  \w   -160.00-131.00   0.50   15.00    --  -90.00 -38.00  60.00   58
 22  \w   -161.00 -84.00   0.50   15.00    --  -90.00 -38.00  90.00  154
 23  \w     96.00 156.00   0.50   15.00    --  108.07  57.00-180.00  120
 24  \w     41.00  66.00   0.50   15.00    --  108.07 -57.00  30.00   50
 25  \w     50.00 102.00   0.50   15.00    --  108.07 -99.00 -90.00  104
 26  \w     38.00 100.00   0.50   15.00    --  108.07 -99.00 -60.00  124
 27  \w     39.00 104.00   0.50   15.00    --  108.07 -77.00  30.00  130
 28  \w    110.00 177.00   0.50   15.00    --  108.07  38.00 -60.00  134
 29  \w    102.00 171.00   0.50   15.00    --  108.07  38.00 -90.00  138
 30  \w     59.00 112.00   0.50   15.00    --  108.07-125.00 150.00  106
 31  \w     39.00  99.00   0.50   15.00    --  108.07-125.00-150.00  120
 32  \w     39.00  97.00   0.50   15.00    --  108.07 -99.00 -30.00  116
 33  \w     36.00  61.00   0.50   15.00    --  108.07 -57.00-150.00   50
 34  \w     50.00 110.00   0.50   15.00    --  108.07-125.00-120.00  120
 35  \w     38.00  63.00   0.50   15.00    --  108.07 -57.00  90.00   50
 36  \w     43.00  73.00   0.50   15.00    --  108.07-125.00  30.00   60
 37  \w     51.00 112.00   0.50   15.00    --  108.07-125.00-180.00  122
 38  \w     85.00 112.00   0.50   15.00    --  108.07-125.00 120.00   54
 39  \w     85.00 112.00   0.50   15.00    --  108.07-125.00  30.00   54
 40  \w     40.00 112.00   0.50   15.00    --  108.07-125.00 -90.00  144
 41  \w     39.00  64.00   0.50   15.00    --  108.07 -57.00-180.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0254737000
_diffrn_orient_matrix_UB_12      -0.0779105000
_diffrn_orient_matrix_UB_13      0.0206878000
_diffrn_orient_matrix_UB_21      0.0225695000
_diffrn_orient_matrix_UB_22      0.0107322000
_diffrn_orient_matrix_UB_23      0.1110514000
_diffrn_orient_matrix_UB_31      -0.1250284000
_diffrn_orient_matrix_UB_32      -0.0139457000
_diffrn_orient_matrix_UB_33      -0.0301574000
_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  0.0341
_diffrn_reflns_av_unetI/netI     0.0173
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            44232
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        66.577
_diffrn_reflns_theta_max         66.576
_diffrn_reflns_theta_min         3.725
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.230
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.25195
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.94a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light violet'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    violet
_exptl_crystal_density_diffrn    1.500
_exptl_crystal_description       block
_exptl_crystal_F_000             1525
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.599
_refine_diff_density_min         -0.825
_refine_diff_density_rms         0.068
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.149
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     399
_refine_ls_number_reflns         5969
_refine_ls_number_restraints     29
_refine_ls_restrained_S_all      1.198
_refine_ls_R_factor_all          0.0293
_refine_ls_R_factor_gt           0.0277
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0211P)^2^+6.4049P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0673
_refine_ls_wR_factor_ref         0.0679
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5704
_reflns_number_total             5969
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07949c3.cif
_cod_data_source_block           exp_7246_auto
_cod_depositor_comments
'Adding full bibliography for 1574113--1574118.cif.'
_cod_original_formula_sum        'C73.60 H56 Cu2 I2 O5.12 P4'
_cod_database_code               1574116
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.459
_shelx_estimated_absorpt_t_min   0.260
_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
2. Restrained distances
 C1-O2
 1.2 with sigma of 0.02
 C1-O1
 1.2 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(O1) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(O2) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.002
4. Rigid body (RIGU) restrains
 O1, C1, O2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
5. Others
 Fixed Sof: C1(0.8)
6.a Aromatic/amide H refined with riding coordinates:
 C007(H007), C00B(H00B), C00E(H00E), C00F(H00F), C00G(H00G), C00H(H00H),
 C00I(H00I), C00L(H00L), C00M(H00M), C00N(H00N), C00O(H00O), C00P(H00P),
 C00Q(H00Q), C00R(H00R), C00S(H00S), C00T(H00T), C00U(H00U), C00V(H00V),
 C00W(H00W), C00X(H00X), C00Y(H00Y), C00Z(H00Z), C010(H010), C011(H011),
 C012(H012), C013(H013), C014(H014), C015(H015)
;
_shelx_res_checksum              50656
_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 2.862
_oxdiff_exptl_absorpt_empirical_full_min 0.710