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_1575276
_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 H68 B N3'
_chemical_formula_sum            'C72 H68 B N3'
_chemical_formula_weight         986.10
_chemical_name_systematic        tCzPAzBN
_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                   11.46318(7)
_cell_length_b                   29.88427(19)
_cell_length_c                   32.13210(17)
_cell_measurement_reflns_used    42158
_cell_measurement_temperature    99.99(10)
_cell_measurement_theta_max      73.1950
_cell_measurement_theta_min      2.7590
_cell_volume                     11007.45(11)
_computing_cell_refinement       'CrysAlisPro 1.171.42.96a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.96a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.96a (Rigaku OD, 2023)'
_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      99.99(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 1.000
_diffrn_measured_fraction_theta_max 0.982
_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    -91.00 -36.00   0.50    0.14    --  -76.67 111.00 120.00  110
  2  \w    -92.00 -31.00   0.50    0.14    --  -76.67 111.00  90.00  122
  3  \w    -75.00 -37.00   0.50    0.14    --  -76.67 111.00   0.00   76
  4  \w    -78.00 -53.00   0.50    0.14    --  -72.12  93.00-175.00   50
  5  \w    -56.00 -19.00   0.50    0.14    --  -59.42  93.00-175.00   74
  6  \w    -64.00 -37.00   0.50    0.14    --  -76.67  93.00-175.00   54
  7  \w   -125.00 -48.00   0.50    0.14    --  -76.67 -15.00-120.00  154
  8  \w   -127.00 -93.00   0.50    0.14    --  -76.67 -15.00-150.00   68
  9  \w   -101.00 -66.00   0.50    0.14    --  -59.42 -15.00-180.00   70
 10  \w   -114.00 -43.00   0.50    0.14    --  -76.67 -15.00 120.00  142
 11  \w     55.00  85.00   0.50    0.14    --   56.39  15.00 -30.00   60
 12  \w     52.00 131.00   0.50    0.14    --   80.61  15.00  60.00  158
 13  \w     36.00  61.00   0.50    0.14    --   80.61-111.00 150.00   50
 14  \w     36.00  90.00   0.50    0.14    --   80.61-111.00  60.00  108
 15  \w     44.00  69.00   0.50    0.14    --   69.64 -95.00 -30.00   50
 16  \w     14.00  62.00   0.50    0.14    --   56.39 -95.00 -30.00   96
 17  \w     38.00  63.00   0.50    0.14    --   80.61 -95.00 150.00   50
 18  \w     16.00  42.00   0.50    0.14    --   56.39 -93.00  72.00   52
 19  \w     28.00  53.00   0.50    0.14    --   69.64 -93.00  72.00   50
 20  \w     43.00  84.00   0.50    0.14    --   80.61 -93.00  72.00   82
 21  \w     39.00  89.00   0.50    0.14    --   80.61-111.00-150.00  100
 22  \w     46.00 129.00   0.50    0.14    --   80.61  15.00-180.00  166
;
_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      -0.1099539000
_diffrn_orient_matrix_UB_12      -0.0296330000
_diffrn_orient_matrix_UB_13      -0.0007015000
_diffrn_orient_matrix_UB_21      -0.0673260000
_diffrn_orient_matrix_UB_22      0.0373837000
_diffrn_orient_matrix_UB_23      -0.0226809000
_diffrn_orient_matrix_UB_31      0.0378725000
_diffrn_orient_matrix_UB_32      -0.0195427000
_diffrn_orient_matrix_UB_33      -0.0422404000
_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  0.0315
_diffrn_reflns_av_unetI/netI     0.0200
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       36
_diffrn_reflns_limit_k_min       -35
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -39
_diffrn_reflns_number            81944
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.254
_diffrn_reflns_theta_min         2.750
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.514
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.91067
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.96a (Rigaku Oxford Diffraction, 2023)
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    1.190
_exptl_crystal_description       block
_exptl_crystal_F_000             4208
_exptl_crystal_preparation       Luminescent
_exptl_crystal_recrystallization_method Sublimation
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.269
_refine_diff_density_min         -0.252
_refine_diff_density_rms         0.039
_refine_ls_extinction_coef       0.000157(15)
_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   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     827
_refine_ls_number_reflns         10846
_refine_ls_number_restraints     445
_refine_ls_restrained_S_all      1.016
_refine_ls_R_factor_all          0.0445
_refine_ls_R_factor_gt           0.0374
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0475P)^2^+3.9190P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0929
_refine_ls_wR_factor_ref         0.0971
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9362
_reflns_number_total             10846
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5mh01084e2.cif
_cod_data_source_block           2312124lt_auto
_cod_depositor_comments
'Adding full bibliography for 1575274--1575276.cif.'
_cod_original_cell_volume        11007.46(11)
_cod_database_code               1575276
_shelx_shelxl_version_number     2018/3
_diffrn_oxdiff_digest_hkl
;
0120d125190abdefbd2c41d051b829b48f8b36
;
_reflns_odcompleteness_completeness 99.94
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     68.13
_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
 C5-C65 \\sim C5-C65A
 with sigma of 0.02
 C65-C66 \\sim C65A-C66A
 with sigma of 0.02
 C65-C70 \\sim C65A-C70A
 with sigma of 0.02
 C66-C67 \\sim C66A-C67A
 with sigma of 0.02
 C70-C69 \\sim C70A-C69A
 with sigma of 0.02
 C68-C69 \\sim C68A-C69A
 with sigma of 0.02
 C68-C67 \\sim C68A-C67A
 with sigma of 0.02
 C5-C66 \\sim C5-C66A
 with sigma of 0.04
 C5-C70 \\sim C5-C70A
 with sigma of 0.04
 C65-C69 \\sim C65A-C69A
 with sigma of 0.04
 C65-C67 \\sim C65A-C67A
 with sigma of 0.04
 C66-C70 \\sim C66A-C70A
 with sigma of 0.04
 C66-C68 \\sim C66A-C68A
 with sigma of 0.04
 C70-C68 \\sim C70A-C68A
 with sigma of 0.04
 C69-C67 \\sim C69A-C67A
 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
 C52-C49 \\sim C52A-C49A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C49 \\sim C50 \\sim C51 \\sim C52 \\sim C49A \\sim C50A \\sim C51A \\sim C52A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C61 \\sim C62 \\sim C63 \\sim C64: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
C65 \\sim C66 \\sim C67 \\sim C68 \\sim C69 \\sim C70 \\sim C65A \\sim C66A
\\sim C67A \\sim C68A \\sim C69A \\sim C70A: 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 C54A \\sim C55A \\sim C56A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(C49) = Uanis(C49A)
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. Same fragment restrains
{C49, C50, C51, C52} sigma for 1-2: 0.02, 1-3: 0.04
as in
{C49A, C50A, C51A, C52A}
6. Others
 Sof(C65A)=Sof(C66A)=Sof(H66A)=Sof(C67A)=Sof(H67A)=Sof(C68A)=Sof(H68A)=
 Sof(C69A)=Sof(H69A)=Sof(C70A)=Sof(H70A)=1-FVAR(1)
 Sof(C65)=Sof(C66)=Sof(H66)=Sof(C67)=Sof(H67)=Sof(C68)=Sof(H68)=Sof(C69)=
 Sof(H69)=Sof(C70)=Sof(H70)=FVAR(1)
 Sof(C53A)=Sof(C54A)=Sof(H54D)=Sof(H54E)=Sof(H54F)=Sof(C55A)=Sof(H55D)=
 Sof(H55E)=Sof(H55F)=Sof(C56A)=Sof(H56D)=Sof(H56E)=Sof(H56F)=1-FVAR(2)
 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(2)
 Sof(C49A)=Sof(C50A)=Sof(H50D)=Sof(H50E)=Sof(H50F)=Sof(C51A)=Sof(H51D)=
 Sof(H51E)=Sof(H51F)=Sof(C52A)=Sof(H52D)=Sof(H52E)=Sof(H52F)=1-FVAR(3)
 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(3)
7.a Everything fixed:
 H26, H57
7.b Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B)
7.c 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),
  C72(H72), C73(H73), C74(H74), C75(H75), C76(H76), C66(H66), C67(H67),
 C68(H68), C69(H69), C70(H70), C66A(H66A), C67A(H67A), C68A(H68A), C69A(H69A),
 C70A(H70A)
7.d 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), C62(H62A,H62B,H62C), C63(H63A,H63B,H63C),
 C64(H64A,H64B,H64C), C50A(H50D,H50E,H50F), C51A(H51D,H51E,H51F), C52A(H52D,
 H52E,H52F), C54A(H54D,H54E,H54F), C55A(H55D,H55E,H55F), C56A(H56D,H56E,H56F)
;
_shelx_res_checksum              43213
_shelx_hkl_checksum              73566
_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 1.259
_oxdiff_exptl_absorpt_empirical_full_min 0.884