Orthogonal Di-Spiro Skeleton Engineering on Suppressing π-π Stacking and Spectral Broadening for High-Performance Narrowband Electroluminescence
Li, Hao-Ze; Yang, Yu-Tao; Zhao, Yi-Cheng; Xie, Feng-Ming; Tang, Jianxin; Li, Yanqing; Materials Horizons  (2025) –; doi:10.1039/D5MH01864A

data_1576312
_publ_section_title
;
 Orthogonal Di-Spiro Skeleton Engineering on Suppressing \p-\p Stacking
 and Spectral Broadening for High-Performance Narrowband
 Electroluminescence
;
_journal_name_full               'Materials Horizons'
_journal_paper_doi               10.1039/D5MH01864A
_journal_year                    2025
_chemical_formula_moiety         'C72 H61 B N2 S, 1[C2H6O], 1.5[C2H6O]'
_chemical_formula_sum            'C77 H76 B N2 O2.5 S'
_chemical_formula_weight         1112.26
_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_creation_date             2025-11-10
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7314)
;
_audit_update_record
;
2025-11-11 deposited with the CCDC.	2025-11-21 downloaded from the CCDC.
;
_cell_angle_alpha                88.548(15)
_cell_angle_beta                 72.501(13)
_cell_angle_gamma                71.849(13)
_cell_formula_units_Z            2
_cell_length_a                   12.865(3)
_cell_length_b                   14.573(3)
_cell_length_c                   18.248(4)
_cell_measurement_reflns_used    7189
_cell_measurement_temperature    170
_cell_measurement_theta_max      63.931
_cell_measurement_theta_min      2.546
_cell_volume                     3091.7(12)
_computing_cell_refinement       'SAINT V8.41 (?, 2016)'
_computing_data_collection       'Bruker APEX III'
_computing_data_reduction        'SAINT V8.41 (?, 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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      170
_diffrn_measured_fraction_theta_full 0.968
_diffrn_measured_fraction_theta_max 0.968
_diffrn_measurement_device_type  'D8 VENTURE'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0900
_diffrn_reflns_av_unetI/netI     0.0869
_diffrn_reflns_Laue_measured_fraction_full 0.968
_diffrn_reflns_Laue_measured_fraction_max 0.968
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            33711
_diffrn_reflns_point_group_measured_fraction_full 0.968
_diffrn_reflns_point_group_measured_fraction_max 0.968
_diffrn_reflns_theta_full        64.080
_diffrn_reflns_theta_max         64.080
_diffrn_reflns_theta_min         2.546
_exptl_absorpt_coefficient_mu    0.847
_exptl_absorpt_correction_T_max  0.7524
_exptl_absorpt_correction_T_min  0.5365
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1358 before and 0.0890 after correction.
The Ratio of minimum to maximum transmission is 0.7131.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.195
_exptl_crystal_description       needle
_exptl_crystal_F_000             1186
_exptl_crystal_size_max          0.09
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.326
_refine_diff_density_min         -0.325
_refine_diff_density_rms         0.046
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.068
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     753
_refine_ls_number_reflns         9945
_refine_ls_number_restraints     132
_refine_ls_restrained_S_all      1.066
_refine_ls_R_factor_all          0.1483
_refine_ls_R_factor_gt           0.0951
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0747P)^2^+3.4104P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2309
_refine_ls_wR_factor_ref         0.2570
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5377
_reflns_number_total             9945
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5mh01864a2.cif
_cod_data_source_block           dsbns_0m
_cod_original_cell_volume        3091.5(11)
_cod_original_formula_sum        'C77 H76 B N2 O2.50 S'
_cod_database_code               1576312
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.983
_shelx_estimated_absorpt_t_min   0.928
_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
 C65-C66 \\sim C65-C66A
 with sigma of 0.02
 C65-C68 \\sim C65-C68A
 with sigma of 0.02
 C65-C67 \\sim C65-C67A
 with sigma of 0.02
 C63-C66 \\sim C63-C66A
 with sigma of 0.04
 C63-C68 \\sim C63-C68A
 with sigma of 0.04
 C63-C67 \\sim C63-C67A
 with sigma of 0.04
 C66-C68 \\sim C66A-C68A
 with sigma of 0.04
 C66-C67 \\sim C66A-C67A
 with sigma of 0.04
 C68-C67 \\sim C68A-C67A
 with sigma of 0.04
3. Rigid bond restraints
 C73, C74, C72, C71, C70, C75
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4. Uiso/Uaniso restraints and constraints
C73 \\sim C75 \\sim C71 \\sim C70 \\sim C72 \\sim C74: within 2A with sigma of
0.005 and sigma for terminal atoms of 0.01 within 2A
Uanis(C68) \\sim Ueq, Uanis(C67) \\sim Ueq: with sigma of 0.1 and sigma for
terminal atoms of 0.2
Uanis(C65) \\sim Ueq, Uanis(C66A) \\sim Ueq, Uanis(C67A) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
5. Rigid body (RIGU) restrains
 C65, C66, C68, C67, C66A, C68A, C67A, C63
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
6. Others
 Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(H75C)=Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(H70C)=
 Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=1-FVAR(1)
 Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(H72C)=Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=
 Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(H73C)=FVAR(1)
 Sof(C66A)=Sof(H66D)=Sof(H66E)=Sof(H66F)=Sof(C68A)=Sof(H68D)=Sof(H68E)=
 Sof(H68F)=Sof(C67A)=Sof(H67D)=Sof(H67E)=Sof(H67F)=1-FVAR(2)
 Sof(C66)=Sof(H66A)=Sof(H66B)=Sof(H66C)=Sof(C68)=Sof(H68A)=Sof(H68B)=Sof(H68C)=
 Sof(C67)=Sof(H67A)=Sof(H67B)=Sof(H67C)=FVAR(2)
7.a Me refined with riding coordinates:
 C66(H66A,H66B,H66C), C68(H68A,H68B,H68C), C67(H67A,H67B,H67C), C66A(H66D,H66E,
 H66F), C68A(H68D,H68E,H68F), C67A(H67D,H67E,H67F)
7.b Aromatic/amide H refined with riding coordinates:
 C49(H49), C54(H54), C52(H52), C50(H50), C29(H29), C51(H51), C62(H62), C7(H7),
 C9(H9), C16(H16), C57(H57), C55(H55), C14(H14), C64(H64), C32(H32), C30(H30),
 C43(H43), C44(H44), C36(H36), C31(H31), C45(H45), C46(H46), C37(H37), C38(H38),
  C39(H39)
7.c Idealised Me refined as rotating group:
 C77(H77A,H77B,H77C), C79(H79A,H79B,H79C), C78(H78A,H78B,H78C), C18(H18A,H18B,
 H18C), C20(H20A,H20B,H20C), C19(H19A,H19B,H19C), C72(H72A,H72B,H72C), C71(H71A,
 H71B,H71C), C73(H73A,H73B,H73C), C75(H75A,H75B,H75C), C70(H70A,H70B,H70C),
 C74(H74A,H74B,H74C)
;
_olex2_submission_special_instructions 'No special instructions were received'