Enhancing the reverse intersystem crossing (RISC) rates and efficiencies of MR-TADF emitters with a U-shaped molecular structure for solution-processed OLEDs.
Xu, Shipan; Liu, Wenping; Yan, An; Du, Xuyang; Sun, Yuanhui; Tao, Junfei; Zhou, Guijiang; Chen, Zhao; Yang, Xiaolong; Chemical science 16 (2025) 19956–19966; doi:10.1039/d5sc04507j

data_1575837
_publ_section_title
;
 Enhancing the reverse intersystem crossing (RISC) rates and efficiencies
 of MR-TADF emitters with a U-shaped molecular structure for
 solution-processed OLEDs.
;
_journal_issue                   42
_journal_name_full               'Chemical science'
_journal_page_first              19956
_journal_page_last               19966
_journal_paper_doi               10.1039/d5sc04507j
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C H2 Cl2, C77 H68 B N5, C Cl'
_chemical_formula_sum            'C79 H70 B Cl3 N5'
_chemical_formula_weight         1206.56
_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_block_doi                 10.5517/ccdc.csd.cc2pdzx0
_audit_creation_date             2024-06-11
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-09-04 deposited with the CCDC.	2025-09-19 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.7380(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.8695(6)
_cell_length_b                   9.7003(2)
_cell_length_c                   30.5929(9)
_cell_measurement_reflns_used    9910
_cell_measurement_temperature    150.00
_cell_measurement_theta_max      27.20
_cell_measurement_theta_min      2.47
_cell_volume                     6563.5(3)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_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  (Sheldrick, 2015)'
_diffrn_ambient_temperature      150.00
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.996
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0860
_diffrn_reflns_av_unetI/netI     0.0683
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       29
_diffrn_reflns_limit_h_min       -29
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            79797
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.497
_diffrn_reflns_theta_min         2.036
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    0.188
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6741
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0723 before and 0.0634 after correction.
The Ratio of minimum to maximum transmission is 0.9041.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.221
_exptl_crystal_description       block
_exptl_crystal_F_000             2540
_exptl_crystal_size_max          0.33
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.25
_refine_diff_density_max         1.646
_refine_diff_density_min         -1.038
_refine_diff_density_rms         0.089
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.096
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     815
_refine_ls_number_reflns         15010
_refine_ls_number_restraints     109
_refine_ls_restrained_S_all      1.167
_refine_ls_R_factor_all          0.1310
_refine_ls_R_factor_gt           0.0875
_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^)+(0.1794P)^2^+0.0991P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2576
_refine_ls_wR_factor_ref         0.2927
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9117
_reflns_number_total             15010
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc04507j2.cif
_cod_data_source_block           xsp_63_0m
_cod_depositor_comments
'Adding full bibliography for 1575837--1575838.cif.'
_cod_database_code               1575837
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Cl2-C79 = Cl3-C80
 1.5 with sigma of 0.01
 Cl3-C80 = Cl2-C79
 1.42 with sigma of 0.01
 Cl4-Cl2
 2.6 with sigma of 0.01
 Cl5-Cl3
 2.6 with sigma of 0.01
 Cl6-C1A
 1.771 with sigma of 0.01
 C39-H39 = C33-H33
 0.93 with sigma of 0.001
 H33-H39 = H59-H37
 2 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
C64 \\sim C66 \\sim C67 \\sim C81: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Cl6 \\sim C1A: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
C13 \\sim C12 \\sim C11 \\sim C10 \\sim C9 \\sim C14: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C66) \\sim Ueq, Uanis(C81) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(Cl4) \\sim Ueq, Uanis(Cl3) \\sim Ueq, Uanis(Cl5) \\sim Ueq, Uanis(Cl2)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C80) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C81) = Uanis(C65) = Uanis(C67) = Uanis(C83) = Uanis(C66) = Uanis(C82)
Uanis(Cl3) = Uanis(Cl4) = Uanis(Cl5) = Uanis(Cl2)
4. Rigid body (RIGU) restrains
 Cl6, C1A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(Cl2)=Sof(C79)=Sof(H79A)=Sof(H79B)=Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=
 Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(H67C)=Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(H81C)=
 Sof(Cl4)=1-FVAR(1)
 Sof(Cl3)=Sof(C80)=Sof(H80A)=Sof(H80B)=Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(H65C)=
 Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(H82C)=Sof(C83)=Sof(H83A)=Sof(H83B)=Sof(H83C)=
 Sof(Cl5)=FVAR(1)
6.a Secondary CH2 refined with riding coordinates:
 C80(H80A,H80B), C79(H79A,H79B)
6.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5), C10(H10), C11(H11), C12(H12),
 C13(H13), C14(H14), C17(H17), C18(H18), C20(H20), C21(H21), C23(H23), C24(H24),
  C25(H25), C27(H27), C28(H28), C29(H29), C33(H33), C37(H37), C39(H39),
 C40(H40), C42(H42), C51(H51), C53(H53), C59(H59), C60(H60), C62(H62), C71(H71),
  C73(H73)
6.c Idealised Me refined as rotating group:
 C45(H45A,H45B,H45C), C46(H46A,H46B,H46C), C47(H47A,H47B,H47C), C55(H55A,H55B,
 H55C), C56(H56A,H56B,H56C), C57(H57A,H57B,H57C), C65(H65A,H65B,H65C), C66(H66A,
 H66B,H66C), C67(H67A,H67B,H67C), C75(H75A,H75B,H75C), C76(H76A,H76B,H76C),
 C77(H77A,H77B,H77C), C81(H81A,H81B,H81C), C82(H82A,H82B,H82C), C83(H83A,H83B,
 H83C)
;
_shelx_res_checksum              84798
_olex2_submission_special_instructions 'No special instructions were received'