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_1574118
_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, 0.8(C O2)'
_chemical_formula_sum            'C72.8 H56 Cu2 I2 O3.6 P4'
_chemical_formula_weight         1493.13
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-10-23
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-10-24 deposited with the CCDC.	2025-03-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 116.9340(10)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   13.45670(10)
_cell_length_b                   19.33800(10)
_cell_length_c                   14.8468(2)
_cell_measurement_reflns_used    28077
_cell_measurement_temperature    291.33(10)
_cell_measurement_theta_max      78.0040
_cell_measurement_theta_min      4.0350
_cell_volume                     3444.44(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 1.5 (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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      air
_diffrn_ambient_temperature      291.33(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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    -95.00 -29.00   0.50    0.73    --  -50.55 138.00 -17.00  132
  2  \w   -118.00 -93.00   0.50    0.73    --  -50.55-138.00 -79.00   50
  3  \w    -84.00 -58.00   0.50    0.73    --  -50.55 132.00 166.00   52
  4  \w   -119.00 -94.00   0.50    0.73    --  -50.55-132.00  97.00   50
  5  \w     44.00  80.00   0.50    0.73    --   50.55-132.00  97.00   72
  6  \w     43.00  68.00   0.50    0.73    --   50.55-138.00 -79.00   50
  7  \w    -78.00 -52.00   0.50    2.90    --  -90.00 132.00 166.00   52
  8  \w   -133.00-107.00   0.50    2.90    --  -90.00-138.00 -79.00   52
  9  \w    -99.00 -72.00   0.50    2.90    --  -90.00-138.00 -79.00   54
 10  \w     81.00 115.00   0.50    2.90    --  108.07-132.00  97.00   68
 11  \w     91.00 151.00   0.50    2.90    --  108.07 132.00 166.00  120
 12  \w    107.00 132.00   0.50    2.90    --  108.07 138.00 -17.00   50
 13  \w     68.00 120.00   0.50    2.90    --  108.07-138.00 -79.00  104
 14  \w   -111.00 -34.00   0.50    0.73    --  -50.55 -77.00 -30.00  154
 15  \w   -122.00 -32.00   0.50    0.73    --  -50.55 -77.00 120.00  180
 16  \w   -106.00 -80.00   0.50    0.73    --  -50.55-125.00 -60.00   52
 17  \w    -15.00  22.00   0.50    0.73    --  -50.55  19.00  90.00   74
 18  \w    -22.00  23.00   0.50    0.73    --  -50.55  19.00-120.00   90
 19  \w   -119.00 -93.00   0.50    0.73    --  -50.55-125.00 -30.00   52
 20  \w   -118.00 -77.00   0.50    0.73    --  -50.55-125.00 120.00   82
 21  \w   -160.00 -98.00   0.50    2.90    --  -90.00 -57.00 -60.00  124
 22  \w   -161.00 -92.00   0.50    2.90    --  -90.00 -38.00 150.00  138
 23  \w    -50.00 -18.00   0.50    2.90    --  -90.00  57.00  30.00   64
 24  \w   -139.00-114.00   0.50    2.90    --  -90.00-132.00  97.00   50
 25  \w   -156.00 -79.00   0.50    2.90    --  -90.00-125.00  60.00  154
 26  \w    108.00 176.00   0.50    2.90    --  108.07  38.00 -30.00  136
 27  \w     48.00  96.00   0.50    2.90    --  108.07-125.00  30.00   96
 28  \w     36.00 105.00   0.50    2.90    --  108.07 -77.00-120.00  138
 29  \w    134.00 178.00   0.50    2.90    --  108.07  57.00  60.00   88
 30  \w    145.00 173.00   0.50    2.90    --  108.07  57.00 -90.00   56
 31  \w    100.00 129.00   0.50    2.90    --  108.07  57.00  60.00   58
 32  \w     37.00  62.00   0.50    2.90    --  108.07 -57.00  60.00   50
 33  \w    105.00 173.00   0.50    2.90    --  108.07  38.00-150.00  136
 34  \w     59.00 104.00   0.50    2.90    --  108.07-125.00   0.00   90
 35  \w     39.00  64.00   0.50    2.90    --  108.07 -57.00 150.00   50
 36  \w     50.00 112.00   0.50    2.90    --  108.07-125.00 120.00  124
 37  \w     38.00  99.00   0.50    2.90    --  108.07 -99.00 120.00  122
 38  \w     40.00  65.00   0.50    2.90    --  108.07 -57.00  90.00   50
 39  \w     45.00  72.00   0.50    2.90    --  108.07 -99.00-180.00   54
 40  \w     80.00 105.00   0.50    2.90    --  108.07 -99.00-180.00   50
 41  \w     36.00  66.00   0.50    2.90    --  108.07 -57.00 -90.00   60
 42  \w     57.00 112.00   0.50    2.90    --  108.07-125.00 -60.00  110
 43  \w     52.00 104.00   0.50    2.90    --  108.07-125.00  60.00  104
 44  \w     37.00  63.00   0.50    2.90    --  108.07 -57.00 -30.00   52
 45  \w    122.00 176.00   0.50    2.90    --  108.07  19.00 -90.00  108
 46  \w     46.00  87.00   0.50    2.90    --  108.07 -99.00 150.00   82
 47  \w     56.00 108.00   0.50    2.90    --  108.07-125.00-150.00  104
 48  \w     41.00  66.00   0.50    2.90    --  108.07 -57.00 -60.00   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      -0.0409634000
_diffrn_orient_matrix_UB_12      0.0592615000
_diffrn_orient_matrix_UB_13      -0.0777408000
_diffrn_orient_matrix_UB_21      0.0448544000
_diffrn_orient_matrix_UB_22      0.0532409000
_diffrn_orient_matrix_UB_23      0.0865850000
_diffrn_orient_matrix_UB_31      0.1131365000
_diffrn_orient_matrix_UB_32      0.0003583000
_diffrn_orient_matrix_UB_33      -0.0026226000
_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  0.0377
_diffrn_reflns_av_unetI/netI     0.0205
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            47254
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        66.601
_diffrn_reflns_theta_max         66.601
_diffrn_reflns_theta_min         3.684
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.031
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.25217
_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_density_diffrn    1.440
_exptl_crystal_description       block
_exptl_crystal_F_000             1491
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.735
_refine_diff_density_min         -0.340
_refine_diff_density_rms         0.058
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.066
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     425
_refine_ls_number_reflns         6071
_refine_ls_number_restraints     72
_refine_ls_restrained_S_all      1.085
_refine_ls_R_factor_all          0.0291
_refine_ls_R_factor_gt           0.0269
_refine_ls_shift/su_max          0.003
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0404P)^2^+1.7320P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0726
_refine_ls_wR_factor_ref         0.0738
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5666
_reflns_number_total             6071
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc07949c3.cif
_cod_data_source_block           exp_7316_auto
_cod_depositor_comments
'Adding full bibliography for 1574113--1574118.cif.'
_cod_original_formula_sum        'C72.80 H56 Cu2 I2 O3.60 P4'
_cod_database_code               1574118
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.265
_shelx_estimated_absorpt_t_min   0.173
_reflns_odcompleteness_completeness 99.84
_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
2. Restrained distances
 O2-C2 = C2-O1
 1.2 with sigma of 0.02
 O1-C2 = C2-O2
 1.2 with sigma of 0.002
 O2-O1
 2.4 with sigma of 0.04
 O1-O2
 2.4 with sigma of 0.004
3. Uiso/Uaniso restraints and constraints
Uanis(C0) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C1) \\sim
Ueq, Uanis(C3) \\sim Ueq, Uanis(C6) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C00Z) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(C011)
\\sim Ueq, Uanis(C2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms
of 0.02
Uanis(O1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(O2) \\sim Ueq: with sigma of
0.001 and sigma for terminal atoms of 0.002
4. Others
 Sof(H01A)=Sof(C0)=Sof(H0)=Sof(C3)=Sof(H3)=Sof(C1)=Sof(H1)=1-FVAR(1)
 Sof(H010)=Sof(C4)=Sof(H4)=Sof(C5)=Sof(H5)=Sof(C6)=Sof(H6)=FVAR(1)
 Fixed Sof: C2(0.4) O1(0.4) O2(0.4)
5.a Aromatic/amide H refined with riding coordinates:
 C008(H008), C00A(H00A), C00D(H00D), C00E(H00E), C00G(H00G), C00H(H00H),
 C00I(H00I), C00J(H00J), 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(H01A), C010(H010),
 C011(H011), C012(H012), C0(H0), C3(H3), C1(H1), C4(H4), C5(H5), C6(H6)
;
_shelx_res_checksum              96178
_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 3.444
_oxdiff_exptl_absorpt_empirical_full_min 0.719