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_1575275
_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         'C72 H58 B D10 N3'
_chemical_formula_sum            'C72 H58 B D10 N3'
_chemical_formula_weight         996.16
_chemical_name_systematic        tCzPAzBN-d10
_space_group_crystal_system      orthorhombic
_space_group_IT_number           61
_space_group_name_Hall           '-P 2ac 2ab'
_space_group_name_H-M_alt        'P b c a'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-07-25
_audit_creation_method
;
Olex2 1.5
(compiled 2025.07.13 svn.rb7424aed for OlexSys, GUI svn.r7311)
;
_audit_update_record
;
2025-07-25 deposited with the CCDC.	2025-07-31 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   11.4583(3)
_cell_length_b                   29.8119(7)
_cell_length_c                   32.0343(11)
_cell_measurement_reflns_used    9992
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      71.7740
_cell_measurement_theta_min      2.7610
_cell_volume                     10942.7(5)
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_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 0.966
_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   -129.00 -91.00   0.50    0.74    --  -77.74 -30.00 150.00   76
  2  \w   -123.00 -78.00   0.50    0.74    --  -68.83 -30.00   0.00   90
  3  \w   -122.00 -96.00   0.50    0.74    --  -77.74 -30.00   0.00   52
  4  \w   -131.00 -84.00   0.50    0.74    --  -77.74 -30.00 -60.00   94
  5  \w   -132.00 -93.00   0.50    0.74    --  -77.74 -30.00 -90.00   78
  6  \w    -43.00 -17.00   0.50    0.74    --  -57.55 110.00  23.00   52
  7  \w    -55.00 -30.00   0.50    0.74    --  -68.83 110.00  23.00   50
  8  \w    -92.00 -40.00   0.50    0.74    --  -77.74 110.00  23.00  104
  9  \w     64.00 106.00   0.50    0.74    --   56.07  30.00 120.00   84
 10  \w     95.00 122.00   0.50    0.74    --   83.09  30.00 150.00   54
 11  \w     95.00 130.00   0.50    0.74    --   83.09  30.00 120.00   70
 12  \w     74.00 122.00   0.50    0.74    --   68.06  30.00  60.00   96
 13  \w     90.00 116.00   0.50    0.74    --   83.09  30.00 -90.00   52
 14  \w     25.00  77.00   0.50    0.74    --   68.06 -95.00 -30.00  104
 15  \w     27.00  66.00   0.50    0.74    --   56.07-110.00 -71.00   78
 16  \w     30.00  55.00   0.50    0.74    --   68.06-110.00 -71.00   50
 17  \w     44.00  69.00   0.50    0.74    --   83.09-110.00 -71.00   50
 18  \w     45.00  87.00   0.50    0.74    --   83.09 -95.00-120.00   84
 19  \w     38.00  84.00   0.50    0.74    --   83.09-111.00-150.00   92
;
_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      -0.0598620000
_diffrn_orient_matrix_UB_12      0.0033018000
_diffrn_orient_matrix_UB_13      0.0429801000
_diffrn_orient_matrix_UB_21      -0.0965066000
_diffrn_orient_matrix_UB_22      0.0294910000
_diffrn_orient_matrix_UB_23      -0.0191548000
_diffrn_orient_matrix_UB_31      -0.0718893000
_diffrn_orient_matrix_UB_32      -0.0422931000
_diffrn_orient_matrix_UB_33      -0.0100391000
_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  0.0331
_diffrn_reflns_av_unetI/netI     0.0295
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.966
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       31
_diffrn_reflns_limit_k_min       -36
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            56669
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.966
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.071
_diffrn_reflns_theta_min         2.759
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.517
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.95423
_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    1.209
_exptl_crystal_description       block
_exptl_crystal_F_000             4208
_exptl_crystal_preparation       Luminescent
_exptl_crystal_recrystallization_method Sublimation
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.08
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.262
_refine_diff_density_min         -0.291
_refine_diff_density_rms         0.050
_refine_ls_extinction_coef       0.00022(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   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     823
_refine_ls_number_reflns         10582
_refine_ls_number_restraints     397
_refine_ls_restrained_S_all      1.035
_refine_ls_R_factor_all          0.0700
_refine_ls_R_factor_gt           0.0505
_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^)+(0.0631P)^2^+5.4926P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1234
_refine_ls_wR_factor_ref         0.1370
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8154
_reflns_number_total             10582
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5mh01084e2.cif
_cod_data_source_block           2507005lt3_auto
_cod_depositor_comments
'Adding full bibliography for 1575274--1575276.cif.'
_cod_original_cell_volume        10942.7(6)
_cod_database_code               1575275
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.970
_shelx_estimated_absorpt_t_min   0.941
_diffrn_oxdiff_digest_hkl
;
4361275ece0ae1c3fe32880a528ffed4bf38ac
;
_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
 C71-C76 \\sim C71-C76A
 with sigma of 0.02
 C46-C49 \\sim C46-C49A
 with sigma of 0.02
 C49-C50 \\sim C49A-C50A
 with sigma of 0.02
 C71-C72 \\sim C71-C72A
 with sigma of 0.02
 C49-C51 \\sim C49A-C51A
 with sigma of 0.02
 C49-C52 \\sim C49A-C52A
 with sigma of 0.02
 C76-C75 \\sim C76A-C75A
 with sigma of 0.02
 C46-C50 \\sim C46-C50A
 with sigma of 0.04
 C46-C51 \\sim C46-C51A
 with sigma of 0.04
 C75-C74 \\sim C75A-C74A
 with sigma of 0.02
 C46-C52 \\sim C46-C52A
 with sigma of 0.04
 C74-C73 \\sim C74A-C73A
 with sigma of 0.02
 C50-C51 \\sim C50A-C51A
 with sigma of 0.04
 C50-C52 \\sim C50A-C52A
 with sigma of 0.04
 C51-C52 \\sim C51A-C52A
 with sigma of 0.04
 C72-C73 \\sim C72A-C73A
 with sigma of 0.02
 C71-C75 \\sim C71-C75A
 with sigma of 0.04
 C71-C73 \\sim C71-C73A
 with sigma of 0.04
 C76-C74 \\sim C76A-C74A
 with sigma of 0.04
 C75-C73 \\sim C75A-C73A
 with sigma of 0.04
 C74-C72 \\sim C74A-C72A
 with sigma of 0.04
 C39-C53 \\sim C39-C53A
 with sigma of 0.02
 C53-C54 \\sim C53A-C54A
 with sigma of 0.02
 C53-C55 \\sim C53A-C55A
 with sigma of 0.02
 C53-C56 \\sim C53A-C56A
 with sigma of 0.02
 C39-C54 \\sim C39-C54A
 with sigma of 0.04
 C39-C55 \\sim C39-C55A
 with sigma of 0.04
 C39-C56 \\sim C39-C56A
 with sigma of 0.04
 C54-C55 \\sim C54A-C55A
 with sigma of 0.04
 C54-C56 \\sim C54A-C56A
 with sigma of 0.04
 C55-C56 \\sim C55A-C56A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C61 \\sim C62 \\sim C63 \\sim C64: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C49 \\sim C50 \\sim C51 \\sim C52 \\sim C49A \\sim C52A \\sim C50A \\sim C51A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C72 \\sim C73 \\sim C74 \\sim C75 \\sim C76 \\sim C72A \\sim C73A \\sim C74A
\\sim C75A \\sim C76A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
C53 \\sim C54 \\sim C55 \\sim C56 \\sim C53A \\sim C56A \\sim C54A \\sim C55A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C63) \\sim Ueq, Uanis(C64) \\sim Ueq, Uanis(C62) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C61, C62, C63, C64
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(C72A)=Sof(D72A)=Sof(C73A)=Sof(D73A)=Sof(C74A)=Sof(D74A)=Sof(C75A)=
 Sof(D75A)=Sof(C76A)=Sof(D76A)=1-FVAR(1)
 Sof(C72)=Sof(D72)=Sof(C73)=Sof(D73)=Sof(C74)=Sof(D74)=Sof(C75)=Sof(D75)=
 Sof(C76)=Sof(D76)=FVAR(1)
 Sof(C49A)=Sof(C52A)=Sof(H52D)=Sof(H52E)=Sof(H52F)=Sof(C50A)=Sof(H50D)=
 Sof(H50E)=Sof(H50F)=Sof(C51A)=Sof(H51D)=Sof(H51E)=Sof(H51F)=1-FVAR(2)
 Sof(C49)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=Sof(C51)=Sof(H51A)=Sof(H51B)=
 Sof(H51C)=Sof(C52)=Sof(H52A)=Sof(H52B)=Sof(H52C)=FVAR(2)
 Sof(C53A)=Sof(C56A)=Sof(H56D)=Sof(H56E)=Sof(H56F)=Sof(C54A)=Sof(H54D)=
 Sof(H54E)=Sof(H54F)=Sof(C55A)=Sof(H55D)=Sof(H55E)=Sof(H55F)=1-FVAR(3)
 Sof(C53)=Sof(C54)=Sof(H54A)=Sof(H54B)=Sof(H54C)=Sof(C55)=Sof(H55A)=Sof(H55B)=
 Sof(H55C)=Sof(C56)=Sof(H56A)=Sof(H56B)=Sof(H56C)=FVAR(3)
6.a Everything fixed:
 H26, H57
6.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B)
6.c Me refined with riding coordinates:
 C62(H62A,H62B,H62C)
6.d Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C11(H11), C13(H13), C14(H14), C24(H24), C29(H29),
 C31(H31), C38(H38), C40(H40), C44(H44), C45(H45), C47(H47), C58(H58), C60(H60),
  C66(D66), C67(D67), C68(D68), C69(D69), C70(D70), C72(D72), C73(D73),
 C74(D74), C75(D75), C76(D76), C72A(D72A), C73A(D73A), C74A(D74A), C75A(D75A),
 C76A(D76A)
6.e Idealised Me refined as rotating group:
 C33(H33A,H33B,H33C), C34(H34A,H34B,H34C), C35(H35A,H35B,H35C), C50(H50A,H50B,
 H50C), C51(H51A,H51B,H51C), C52(H52A,H52B,H52C), C54(H54A,H54B,H54C), C55(H55A,
 H55B,H55C), C56(H56A,H56B,H56C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C),
 C52A(H52D,H52E,H52F), C50A(H50D,H50E,H50F), C51A(H51D,H51E,H51F), C56A(H56D,
 H56E,H56F), C54A(H54D,H54E,H54F), C55A(H55D,H55E,H55F)
;
_shelx_res_checksum              19994
_shelx_hkl_checksum              73022
_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 1.130
_oxdiff_exptl_absorpt_empirical_full_min 0.895