Strategic azepine engineering realizes highly efficient and stable blue narrowband light-emitting diodes.
Chen, Yi-Kuan; Lei, Jian; Chao, Yu-Chieh; Kung, Yu-Cheng; Hung, Wen-Yi; Hsu, Liang-Yan; Wu, Tien-Lin; Materials horizons 12 (2025) 9737–9748; doi:10.1039/d5mh01084e

data_1575274
_publ_section_title
;
 Strategic azepine engineering realizes highly efficient and stable blue
 narrowband light-emitting diodes.
;
_journal_issue                   22
_journal_name_full               'Materials horizons'
_journal_page_first              9737
_journal_page_last               9748
_journal_paper_doi               10.1039/d5mh01084e
_journal_volume                  12
_journal_year                    2025
_chemical_formula_moiety         'C60 H60 B N3'
_chemical_formula_sum            'C60 H60 B N3'
_chemical_formula_weight         833.92
_chemical_name_systematic        tCzAzBN
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-07-08
_audit_creation_method
;
Olex2 1.5
(compiled 2025.05.31 svn.r86d253d1 for OlexSys, GUI svn.r7254)
;
_audit_update_record
;
2025-07-11 deposited with the CCDC.	2025-07-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 101.820(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   15.8245(7)
_cell_length_b                   9.6398(5)
_cell_length_c                   32.5330(14)
_cell_measurement_reflns_used    5876
_cell_measurement_temperature    100.00(15)
_cell_measurement_theta_max      66.9090
_cell_measurement_theta_min      2.7560
_cell_volume                     4857.5(4)
_computing_cell_refinement       'CrysAlisPro 1.171.44.113a (Rigaku OD, 2025)'
_computing_data_collection       'CrysAlisPro 1.171.44.113a (Rigaku OD, 2025)'
_computing_data_reduction        'CrysAlisPro 1.171.44.113a (Rigaku OD, 2025)'
_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_environment      N~2~
_diffrn_ambient_temperature      100.00(15)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.962
_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     12.00  64.00   0.50    5.70    --   56.07 -95.00  60.00  104
  2  \w     11.00  36.00   0.50    5.70    --   56.07 -95.00-120.00   50
  3  \w   -102.00 -65.00   0.50    5.70    --  -57.24 -30.00   0.00   74
  4  \w   -105.00 -72.00   0.50    5.70    --  -57.24 -30.00  30.00   66
  5  \w     42.00  69.00   0.50    5.70    --   68.06 -95.00-120.00   54
  6  \w     90.00 121.00   0.50    5.70    --   68.06  30.00 -30.00   62
  7  \w    -78.00 -33.00   0.50    5.70    --  -68.39 125.00 -30.00   90
  8  \w   -129.00 -91.00   0.50    5.70    --  -77.74 -15.00 -90.00   76
  9  \w   -127.00 -86.00   0.50    5.70    --  -77.74 -30.00  30.00   82
 10  \w    -88.00 -49.00   0.50    5.70    --  -77.74 -15.00 -90.00   78
 11  \w   -132.00 -97.00   0.50    5.70    --  -77.74 -30.00   0.00   70
 12  \w   -125.00 -84.00   0.50    5.70    --  -77.74 -30.00  60.00   82
 13  \w    -87.00 -27.00   0.50    5.70    --  -77.74 111.00 -90.00  120
 14  \w   -130.00 -50.00   0.50    5.70    --  -77.74 -15.00-180.00  160
 15  \w     94.00 135.00   0.50    5.70    --   83.09  30.00   0.00   82
 16  \w     89.00 117.00   0.50    5.70    --   83.09  30.00-150.00   56
 17  \w     38.00  63.00   0.50    5.70    --   83.09 -95.00 -60.00   50
 18  \w     39.00  71.00   0.50    5.70    --   83.09 -95.00  60.00   64
 19  \w    105.00 130.00   0.50    5.70    --   83.09  30.00 -90.00   50
 20  \w     55.00  89.00   0.50    5.70    --   83.09 -95.00-120.00   68
 21  \w     97.00 137.00   0.50    5.70    --   83.09  30.00 -60.00   80
 22  \w     48.00  85.00   0.50    5.70    --   83.09-111.00  90.00   74
 23  \w     96.00 132.00   0.50    5.70    --   83.09  30.00 150.00   72
 24  \w     39.00  79.00   0.50    5.70    --   83.09 -95.00-150.00   80
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0771752000
_diffrn_orient_matrix_UB_12      0.0225082000
_diffrn_orient_matrix_UB_13      0.0368487000
_diffrn_orient_matrix_UB_21      0.0349530000
_diffrn_orient_matrix_UB_22      0.1140143000
_diffrn_orient_matrix_UB_23      -0.0252230000
_diffrn_orient_matrix_UB_31      -0.0522252000
_diffrn_orient_matrix_UB_32      0.1094904000
_diffrn_orient_matrix_UB_33      0.0186558000
_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  0.0473
_diffrn_reflns_av_unetI/netI     0.0621
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.962
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       39
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            32169
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.962
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.158
_diffrn_reflns_theta_min         2.775
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.494
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.93997
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.44.113a (Rigaku Oxford Diffraction, 2025)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.140
_exptl_crystal_description       plate
_exptl_crystal_F_000             1784
_exptl_crystal_preparation       Luminescent
_exptl_crystal_recrystallization_method Sublimation
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.481
_refine_diff_density_min         -0.512
_refine_diff_density_rms         0.123
_refine_ls_extinction_coef       0.0022(2)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     740
_refine_ls_number_reflns         9334
_refine_ls_number_restraints     336
_refine_ls_restrained_S_all      1.013
_refine_ls_R_factor_all          0.1235
_refine_ls_R_factor_gt           0.0711
_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^)+(0.1313P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1816
_refine_ls_wR_factor_ref         0.2198
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5302
_reflns_number_total             9334
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5mh01084e2.cif
_cod_data_source_block           2507006lt_auto
_cod_depositor_comments
'Adding full bibliography for 1575274--1575276.cif.'
_cod_database_code               1575274
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.981
_shelx_estimated_absorpt_t_min   0.952
_diffrn_oxdiff_digest_hkl
;
431a7941f9a33704697e704bf85dd59b96d99a
;
_diffrn_oxdiff_digest_od_ed
;

;
_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
 C33-C34 \\sim C33-C34A
 with sigma of 0.02
 C21-C23 \\sim C21-C23A
 with sigma of 0.02
 C34-C35 \\sim C34A-C35A
 with sigma of 0.02
 C8-C23 \\sim C8-C23A
 with sigma of 0.04
 C22-C23 \\sim C22A-C23A
 with sigma of 0.04
 C35-C36 \\sim C35A-C36
 with sigma of 0.02
 C33-C35 \\sim C33-C35A
 with sigma of 0.04
 C23-C24 \\sim C23A-C24A
 with sigma of 0.04
 C34-C36 \\sim C34A-C36
 with sigma of 0.04
 C13-C17 \\sim C13-C17A
 with sigma of 0.02
 C17-C18 \\sim C17A-C18A
 with sigma of 0.02
 C17-C19 \\sim C17A-C19A
 with sigma of 0.02
 C17-C20 \\sim C17A-C20A
 with sigma of 0.02
 C13-C18 \\sim C13-C18A
 with sigma of 0.04
 C13-C19 \\sim C13-C19A
 with sigma of 0.04
 C13-C20 \\sim C13-C20A
 with sigma of 0.04
 C18-C19 \\sim C18A-C19A
 with sigma of 0.04
 C18-C20 \\sim C18A-C20A
 with sigma of 0.04
 C19-C20 \\sim C19A-C20A
 with sigma of 0.04
 C61-C62 \\sim C61-C62A
 with sigma of 0.02
 C61-C63 \\sim C61-C63A
 with sigma of 0.02
 C61-C64 \\sim C61-C64A
 with sigma of 0.02
 C48-C62 \\sim C48-C62A
 with sigma of 0.04
 C48-C63 \\sim C48-C63A
 with sigma of 0.04
 C48-C64 \\sim C48-C64A
 with sigma of 0.04
 C62-C63 \\sim C62A-C63A
 with sigma of 0.04
 C62-C64 \\sim C62A-C64A
 with sigma of 0.04
 C63-C64 \\sim C63A-C64A
 with sigma of 0.04
 C57-C58 \\sim C57-C58A
 with sigma of 0.02
 C57-C59 \\sim C57-C59A
 with sigma of 0.02
 C57-C60 \\sim C57-C60A
 with sigma of 0.02
 C55-C58 \\sim C55-C58A
 with sigma of 0.04
 C55-C59 \\sim C55-C59A
 with sigma of 0.04
 C55-C60 \\sim C55-C60A
 with sigma of 0.04
 C58-C59 \\sim C58A-C59A
 with sigma of 0.04
 C58-C60 \\sim C58A-C60A
 with sigma of 0.04
 C59-C60 \\sim C59A-C60A
 with sigma of 0.04
 C21-C22 \\sim C21-C22A
 with sigma of 0.02
 C21-C24 \\sim C21-C24A
 with sigma of 0.02
 C8-C22 \\sim C8-C22A
 with sigma of 0.04
 C8-C24 \\sim C8-C24A
 with sigma of 0.04
 C22-C24 \\sim C22A-C24A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C21 \\sim C22 \\sim C23 \\sim C24 \\sim C22A \\sim C23A \\sim C24A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C35 \\sim C34A \\sim C35A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C17 \\sim C18 \\sim C19 \\sim C20 \\sim C17A \\sim C18A \\sim C19A \\sim C20A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C61 \\sim C62 \\sim C63 \\sim C64 \\sim C62A \\sim C63A \\sim C64A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C57 \\sim C58 \\sim C59 \\sim C60 \\sim C58A \\sim C59A \\sim C60A: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Others
 Sof(C34A)=Sof(H34C)=Sof(H34D)=Sof(C35A)=Sof(H35C)=Sof(H35D)=1-FVAR(1)
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(C35)=Sof(H35A)=Sof(H35B)=FVAR(1)
 Sof(C17A)=Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C19A)=Sof(H19D)=
 Sof(H19E)=Sof(H19F)=Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=1-FVAR(2)
 Sof(C17)=Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C19)=Sof(H19A)=Sof(H19B)=
 Sof(H19C)=Sof(C20)=Sof(H20A)=Sof(H20B)=Sof(H20C)=FVAR(2)
 Sof(C62A)=Sof(H62D)=Sof(H62E)=Sof(H62F)=Sof(C63A)=Sof(H63D)=Sof(H63E)=
 Sof(H63F)=Sof(C64A)=Sof(H64D)=Sof(H64E)=Sof(H64F)=1-FVAR(3)
 Sof(C62)=Sof(H62A)=Sof(H62B)=Sof(H62C)=Sof(C63)=Sof(H63A)=Sof(H63B)=Sof(H63C)=
 Sof(C64)=Sof(H64A)=Sof(H64B)=Sof(H64C)=FVAR(3)
 Sof(C58A)=Sof(H58D)=Sof(H58E)=Sof(H58F)=Sof(C59A)=Sof(H59D)=Sof(H59E)=
 Sof(H59F)=Sof(C60A)=Sof(H60D)=Sof(H60E)=Sof(H60F)=1-FVAR(4)
 Sof(C58)=Sof(H58A)=Sof(H58B)=Sof(H58C)=Sof(C59)=Sof(H59A)=Sof(H59B)=Sof(H59C)=
 Sof(C60)=Sof(H60A)=Sof(H60B)=Sof(H60C)=FVAR(4)
 Sof(C22A)=Sof(H22D)=Sof(H22E)=Sof(H22F)=Sof(C23A)=Sof(H23D)=Sof(H23E)=
 Sof(H23F)=Sof(C24A)=Sof(H24D)=Sof(H24E)=Sof(H24F)=1-FVAR(5)
 Sof(C22)=Sof(H22A)=Sof(H22B)=Sof(H22C)=Sof(C23)=Sof(H23A)=Sof(H23B)=Sof(H23C)=
 Sof(C24)=Sof(H24A)=Sof(H24B)=Sof(H24C)=FVAR(5)
5.a Everything fixed:
 H42, H25, H15, H53
5.b Secondary CH2 refined with riding coordinates:
 C34(H34A,H34B), C35(H35A,H35B), C34A(H34C,H34D), C35A(H35C,H35D)
5.c Me refined with riding coordinates:
 C23(H23A,H23B,H23C), C23A(H23D,H23E,H23F)
5.d Aromatic/amide H refined with riding coordinates:
 C7(H7), C9(H9), C12(H12), C14(H14), C29(H29), C30(H30), C31(H31), C32(H32),
 C37(H37), C38(H38), C39(H39), C40(H40), C47(H47), C49(H49), C54(H54), C56(H56)
5.e Idealised Me refined as rotating group:
 C18(H18A,H18B,H18C), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C22(H22A,H22B,
 H22C), C24(H24A,H24B,H24C), C58(H58A,H58B,H58C), C59(H59A,H59B,H59C), C60(H60A,
 H60B,H60C), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C),
 C18A(H18D,H18E,H18F), C19A(H19D,H19E,H19F), C20A(H20D,H20E,H20F), C22A(H22D,
 H22E,H22F), C24A(H24D,H24E,H24F), C58A(H58D,H58E,H58F), C59A(H59D,H59E,H59F),
 C60A(H60D,H60E,H60F), C62A(H62D,H62E,H62F), C63A(H63D,H63E,H63F), C64A(H64D,
 H64E,H64F)
;
_shelx_res_checksum              82738
_shelx_hkl_checksum              30835
_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 1.193
_oxdiff_exptl_absorpt_empirical_full_min 0.890