TADF-emitting copper(i) and silver(i) complexes featuring intra-ligand charge transfer based on a donor–acceptor–donor ligand
Wang, Xinwei; Li, Weijun; Li, Xiao; Hou, Chenlu; Wei, Sanyue; Lei, Wenxin; Chen, Xu-Lin; New Journal of Chemistry 49 (2025) 755–760; doi:10.1039/D4NJ04193C

data_1573391
_publ_section_title
;
 TADF-emitting copper(i) and silver(i) complexes featuring intra-ligand
 charge transfer based on a donor--acceptor--donor ligand
;
_journal_issue                   3
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              755
_journal_page_last               760
_journal_paper_doi               10.1039/D4NJ04193C
_journal_volume                  49
_journal_year                    2025
_chemical_formula_moiety         '(C81 H66 Cu N4 O P2), (B F4), 1.5(C4 H10 O)'
_chemical_formula_sum            'C87 H81 B Cu F4 N4 O2.5 P2'
_chemical_formula_weight         1434.92
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-11-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-12-01 deposited with the CCDC.	2024-12-04 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.466(5)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   19.927(3)
_cell_length_b                   21.694(3)
_cell_length_c                   34.974(6)
_cell_measurement_reflns_used    9906
_cell_measurement_temperature    200(2)
_cell_measurement_theta_max      23.97
_cell_measurement_theta_min      2.23
_cell_volume                     14640(4)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_collection       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      200.0
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0997
_diffrn_reflns_av_unetI/netI     0.0520
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            91109
_diffrn_reflns_point_group_measured_fraction_full 0.995
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        24.498
_diffrn_reflns_theta_max         24.498
_diffrn_reflns_theta_min         1.971
_exptl_absorpt_coefficient_mu    0.406
_exptl_absorpt_correction_T_max  0.7451
_exptl_absorpt_correction_T_min  0.6696
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0869 before and 0.0686 after correction.
The Ratio of minimum to maximum transmission is 0.8987.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.302
_exptl_crystal_description       block
_exptl_crystal_F_000             5504
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.566
_refine_diff_density_min         -0.936
_refine_diff_density_rms         0.074
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.040
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     736
_refine_ls_number_reflns         12127
_refine_ls_number_restraints     220
_refine_ls_restrained_S_all      1.059
_refine_ls_R_factor_all          0.1146
_refine_ls_R_factor_gt           0.0779
_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^)+(0.1271P)^2^+40.2486P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2148
_refine_ls_wR_factor_ref         0.2459
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7996
_reflns_number_total             12127
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4nj04193c2.cif
_cod_data_source_block           mo_cu_11_0m
_cod_depositor_comments
'Adding full bibliography for 1573391--1573392.cif.'
_cod_database_code               1573391
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.954
_shelx_estimated_absorpt_t_min   0.943
_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. Restrained distances
 C57A-C58A = C58A-C59A = C57B-C58B = C58B-C59B
 1.54 with sigma of 0.02
 C57A-C59A = C57B-C59B
 2.55 with sigma of 0.02
 N7A-C52A = N7A-C60A = N7B-C52B = N7B-C60B
 1.47 with sigma of 0.02
 C52A-C60A = C52B-C60B
 2.46 with sigma of 0.02
 C58A-C65A = C58A-C66A = C58B-C65B = C58B-C66B
 1.54 with sigma of 0.02
 C65A-C66A = C65A-C57A = C65A-C59A = C66A-C57A = C66A-C59A
 2.53 with sigma of 0.02
 C65B-C66B = C65B-C57B = C65B-C59B = C66B-C57B = C66B-C59B
 2.53 with sigma of 0.02
 B1A-F1A = B1A-F2A = B1A-F3A = B1A-F4A
 1.27 with sigma of 0.02
 B1B-F1B = B1B-F2B = B1B-F3B = B1B-F4B
 1.27 with sigma of 0.02
 F1A-F2A = F1A-F3A = F1A-F4A = F2A-F3A = F2A-F4A = F3A-F4A
 2.1 with sigma of 0.02
 F1B-F2B = F1B-F3B = F1B-F4B = F2B-F3B = F2B-F4B = F3B-F4B
 2.1 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C19A) \\sim Ueq, Uanis(C20A) \\sim Ueq, Uanis(C21A) \\sim Ueq,
Uanis(C22A) \\sim Ueq, Uanis(C23A) \\sim Ueq, Uanis(C24A) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.01
Uanis(C19B) \\sim Ueq, Uanis(C20B) \\sim Ueq, Uanis(C21B) \\sim Ueq,
Uanis(C22B) \\sim Ueq, Uanis(C23B) \\sim Ueq, Uanis(C24B) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.01
Uanis(C58A) \\sim Ueq, Uanis(C65A) \\sim Ueq, Uanis(C66A) \\sim Ueq,
Uanis(C58B) \\sim Ueq, Uanis(C65B) \\sim Ueq, Uanis(C66B) \\sim Ueq: with sigma
of 0.02 and sigma for terminal atoms of 0.01
Uanis(B1A) \\sim Ueq, Uanis(F1A) \\sim Ueq, Uanis(F2A) \\sim Ueq, Uanis(F3A)
\\sim Ueq, Uanis(F4A) \\sim Ueq: with sigma of 0.02 and sigma for terminal
atoms of 0.01
Uanis(B1B) \\sim Ueq, Uanis(F1B) \\sim Ueq, Uanis(F2B) \\sim Ueq, Uanis(F3B)
\\sim Ueq, Uanis(F4B) \\sim Ueq: with sigma of 0.02 and sigma for terminal
atoms of 0.01
Uanis(C77) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.01
Uanis(C13A) = Uanis(C14A) = Uanis(C15A) = Uanis(C16A) = Uanis(C17A) =
Uanis(C18A)
Uanis(C13B) = Uanis(C14B) = Uanis(C15B) = Uanis(C16B) = Uanis(C17B) =
Uanis(C18B)
Uanis(C19B) = Uanis(C20B) = Uanis(C21B) = Uanis(C22B) = Uanis(C23B) =
Uanis(C24B)
Uanis(C19A) = Uanis(C20A) = Uanis(C21A) = Uanis(C22A) = Uanis(C23A) =
Uanis(C24A)
Uanis(C52A) = Uanis(C52B)
Uanis(C52A) = Uanis(C53A) = Uanis(C54A) = Uanis(C55A) = Uanis(C56A) =
Uanis(C57A)
Uanis(C52B) = Uanis(C53B) = Uanis(C54B) = Uanis(C55B) = Uanis(C56B) =
Uanis(C57B)
Uanis(C60A) = Uanis(C60B)
Uanis(C59A) = Uanis(C60A) = Uanis(C61A) = Uanis(C62A) = Uanis(C63A) =
Uanis(C64A)
Uanis(C59B) = Uanis(C60B) = Uanis(C61B) = Uanis(C62B) = Uanis(C63B) =
Uanis(C64B)
Uanis(C58A) = Uanis(C58B)
Uanis(N7A) = Uanis(N7B)
Uanis(C65A) = Uanis(C65B)
Uanis(C66A) = Uanis(C66B)
Uanis(B1A) = Uanis(F1A) = Uanis(F2A) = Uanis(F3A) = Uanis(F4A)
Uanis(B1B) = Uanis(F1B) = Uanis(F2B) = Uanis(F3B) = Uanis(F4B)
4. Others
 Sof(C13B)=Sof(C14B)=Sof(H14B)=Sof(C15B)=Sof(H15B)=Sof(C16B)=Sof(H16B)=
 Sof(C17B)=Sof(H17B)=Sof(C18B)=Sof(H18B)=1-FVAR(1)
 Sof(C13A)=Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(H15A)=Sof(C16A)=Sof(H16A)=
 Sof(C17A)=Sof(H17A)=Sof(C18A)=Sof(H18A)=FVAR(1)
 Sof(C19B)=Sof(C20B)=Sof(H20B)=Sof(C21B)=Sof(H21B)=Sof(C22B)=Sof(H22B)=
 Sof(C23B)=Sof(H23B)=Sof(C24B)=Sof(H24B)=1-FVAR(2)
 Sof(C19A)=Sof(C20A)=Sof(H20A)=Sof(C21A)=Sof(H21A)=Sof(C22A)=Sof(H22A)=
 Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24A)=FVAR(2)
 Sof(N7B)=Sof(C52B)=Sof(C53B)=Sof(H53B)=Sof(C54B)=Sof(H54B)=Sof(C55B)=
 Sof(H55B)=Sof(C56B)=Sof(H56B)=Sof(C57B)=Sof(C58B)=Sof(C59B)=Sof(C60B)=
 Sof(C61B)=Sof(H61B)=Sof(C62B)=Sof(H62B)=Sof(C63B)=Sof(H63B)=Sof(C64B)=
 Sof(H64B)=Sof(C65B)=Sof(H65D)=Sof(H65E)=Sof(H65F)=Sof(C66B)=Sof(H66D)=
 Sof(H66E)=Sof(H66F)=1-FVAR(3)
 Sof(N7A)=Sof(C52A)=Sof(C53A)=Sof(H53A)=Sof(C54A)=Sof(H54A)=Sof(C55A)=
 Sof(H55A)=Sof(C56A)=Sof(H56A)=Sof(C57A)=Sof(C58A)=Sof(C59A)=Sof(C60A)=
 Sof(C61A)=Sof(H61A)=Sof(C62A)=Sof(H62A)=Sof(C63A)=Sof(H63A)=Sof(C64A)=
 Sof(H64A)=Sof(C65A)=Sof(H65A)=Sof(H65B)=Sof(H65C)=Sof(C66A)=Sof(H66A)=
 Sof(H66B)=Sof(H66C)=FVAR(3)
 Sof(B1B)=Sof(F1B)=Sof(F2B)=Sof(F3B)=Sof(F4B)=1-FVAR(4)
 Sof(B1A)=Sof(F1A)=Sof(F2A)=Sof(F3A)=Sof(F4A)=FVAR(4)
5.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C14A(H14A), C15A(H15A), C16A(H16A), C17A(H17A), C18A(H18A),
 C20A(H20A), C21A(H21A), C22A(H22A), C23A(H23A), C24A(H24A), C26(H26), C27(H27),
  C28(H28), C33(H33), C34(H34), C35(H35), C40(H40), C41(H41), C48(H48),
 C49(H49), C50(H50), C51(H51), C53A(H53A), C54A(H54A), C55A(H55A), C56A(H56A),
 C61A(H61A), C62A(H62A), C63A(H63A), C64A(H64A), C68(H68), C69(H69), C70(H70),
 C71(H71), C75(H75), C76(H76), C77(H77), C78(H78), C14B(H14B), C15B(H15B),
 C16B(H16B), C17B(H17B), C18B(H18B), C20B(H20B), C21B(H21B), C22B(H22B),
 C23B(H23B), C24B(H24B), C53B(H53B), C54B(H54B), C55B(H55B), C56B(H56B),
 C61B(H61B), C62B(H62B), C63B(H63B), C64B(H64B)
5.b Fitted hexagon refined as free rotating group:
 C13A(C14A,C15A,C16A,C17A,C18A), C19A(C20A,C21A,C22A,C23A,C24A), C52A(C53A,
 C54A,C55A,C56A,C57A), C59A(C60A,C61A,C62A,C63A,C64A), C13B(C14B,C15B,C16B,C17B,
 C18B), C19B(C20B,C21B,C22B,C23B,C24B), C52B(C53B,C54B,C55B,C56B,C57B),
 C59B(C60B,C61B,C62B,C63B,C64B)
5.c Idealised Me refined as rotating group:
 C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C65A(H65A,H65B,H65C), C66A(H66A,
 H66B,H66C), C80(H80A,H80B,H80C), C81(H81A,H81B,H81C), C65B(H65D,H65E,H65F),
 C66B(H66D,H66E,H66F)
;
_shelx_res_checksum              34870
_shelx_fab_checksum              81290
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'