Dual-channel deep-NIR-emissive N-embedded PAHs with hybridized local and charge-transfer excited-state.
Li, Zuhao; Zhou, Zhiruo; Yang, Kun; Yao, Yifan; Zhai, Yaxin; Wang, Dong; Zeng, Zebing; Chemical science 16 (2025) 16792–16800; doi:10.1039/d5sc01897h

data_1575950
_publ_section_title
;
 Dual-channel deep-NIR-emissive N-embedded PAHs with hybridized local and
 charge-transfer excited-state.
;
_journal_issue                   36
_journal_name_full               'Chemical science'
_journal_page_first              16792
_journal_page_last               16800
_journal_paper_doi               10.1039/d5sc01897h
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         '0.8(C H2 Cl2), C60 H50 N2 O2'
_chemical_formula_sum            'C60.8 H51.6 Cl1.6 N2 O2'
_chemical_formula_weight         898.96
_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   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2023-03-25
_audit_creation_method
;
Olex2 1.5
(compiled 2021.10.07 svn.r9718050b for OlexSys, GUI svn.r6410)
;
_audit_update_record
;
2025-01-04 deposited with the CCDC.	2025-08-05 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 116.939(5)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   25.3554(12)
_cell_length_b                   7.6892(2)
_cell_length_c                   25.5978(10)
_cell_measurement_reflns_used    3499
_cell_measurement_temperature    99.97(17)
_cell_measurement_theta_max      71.6010
_cell_measurement_theta_min      3.4690
_cell_volume                     4449.1(4)
_computing_cell_refinement       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.46 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      99.97(17)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 8.0697
_diffrn_detector_type            EosS2
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -35.00  95.00   1.00    5.00    --   34.23   0.00 120.00  130
  2  \w     88.00 172.00   1.00   18.00    --  105.88  45.00 120.00   84
  3  \w    124.00 167.00   1.00   18.00    --  105.88  61.00  90.00   43
  4  \w     92.00 127.00   1.00   18.00    --  105.88 -30.00 -60.00   35
  5  \w     91.00 118.00   1.00   18.00    --  105.88  61.00  90.00   27
  6  \w     36.00  75.00   1.00   18.00    --  105.88 -30.00 -60.00   39
  7  \w     45.00 122.00   1.00   18.00    --  105.88 -61.00 -30.00   77
  8  \w     43.00 117.00   1.00   18.00    --  105.88 -45.00-180.00   74
  9  \w     25.00  73.00   1.00    5.00    --   34.23-125.00-120.00   48
 10  \w     26.00  61.00   1.00    5.00    --   34.23-125.00  90.00   35
 11  \w     14.00  41.00   1.00    5.00    --   34.23 -99.00 120.00   27
 12  \w     -7.00  49.00   1.00    5.00    --   34.23 -57.00  90.00   56
 13  \w     37.00 143.00   1.00   18.00    --  105.88 -15.00 120.00  106
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, EosS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0638808000
_diffrn_orient_matrix_UB_12      -0.0575886000
_diffrn_orient_matrix_UB_13      0.0170026000
_diffrn_orient_matrix_UB_21      -0.0229990000
_diffrn_orient_matrix_UB_22      -0.1239354000
_diffrn_orient_matrix_UB_23      -0.0530814000
_diffrn_orient_matrix_UB_31      0.0057753000
_diffrn_orient_matrix_UB_32      0.1464107000
_diffrn_orient_matrix_UB_33      -0.0381781000
_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  0.0247
_diffrn_reflns_av_unetI/netI     0.0736
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       30
_diffrn_reflns_limit_h_min       -28
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -6
_diffrn_reflns_limit_l_max       30
_diffrn_reflns_limit_l_min       -30
_diffrn_reflns_number            14712
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        66.599
_diffrn_reflns_theta_max         66.599
_diffrn_reflns_theta_min         3.317
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.478
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.89227
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.46 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.342
_exptl_crystal_description       block
_exptl_crystal_F_000             1894
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.16
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.514
_refine_diff_density_min         -0.500
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     840
_refine_ls_number_reflns         7825
_refine_ls_number_restraints     1492
_refine_ls_restrained_S_all      1.099
_refine_ls_R_factor_all          0.1455
_refine_ls_R_factor_gt           0.0923
_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^)+(0.0100P)^2^+7.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1543
_refine_ls_wR_factor_ref         0.1744
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3978
_reflns_number_total             7825
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01897h2.cif
_cod_data_source_block           exp_2589
_cod_original_cell_volume        4449.1(3)
_cod_original_formula_sum        'C60.80 H51.60 Cl1.60 N2 O2'
_cod_database_code               1575950
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'C50 H100 O2 N2'
_shelx_estimated_absorpt_t_max   0.809
_shelx_estimated_absorpt_t_min   0.777
_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
 Cl10-C61
 1.77 with sigma of 0.02
 Cl11-C61
 1.78 with sigma of 0.02
 Cl11-C61 = Cl10-C61
 1.771 with sigma of 0.01
 Cl1A-C61A
 1.78 with sigma of 0.02
 Cl11-Cl10
 2.916 with sigma of 0.03
 C5-C26 = C5-C26A = C27-C26 = C27-C26A = C26A-C25 = C24-C23A = C23A-C22 = C23-
 C22 = C24A-C23 = C64-C24A = C64-C26
 1.4 with sigma of 0.01
 Cl2A-C61A
 1.77 with sigma of 0.02
 C12A-C11 = C12-C11 = C13-C12 = C63-C12A = C63-C62 = C62-C19A = C19-C18 = C28-
 C19A = C28-C19 = C20-C19 = C20-C19A
 1.4 with sigma of 0.01
 Cl1A-C61A = Cl2A-C61A
 1.771 with sigma of 0.01
 C26A-C25
 1.385 with sigma of 0.0001
 Cl1A-Cl2A
 2.916 with sigma of 0.03
 Cl2B-Cl1B
 2.916 with sigma of 0.03
 C17A-C16A = C25-C17A = C16A-C15A = C15A-C14A = C24-C14A = C25-C24 = C18-C13 =
 C14-C13 = C15-C14 = C16-C15 = C17-C16 = C18-C17
 1.39 with sigma of 0.003
 Cl2B-C61B = Cl1B-C61B
 1.771 with sigma of 0.01
 Cl1B-C61B
 1.77 with sigma of 0.02
 C16A-C14A
 2.39 with sigma of 0.01
 Cl2B-C61B
 1.78 with sigma of 0.02
 C15A-C24
 2.39 with sigma of 0.01
 Cl2C-C61C
 1.78 with sigma of 0.02
 C14A-C25
 2.39 with sigma of 0.01
 C24-C17A
 2.39 with sigma of 0.01
 Cl2C-C61C = Cl1C-C61C
 1.771 with sigma of 0.01
 C25-C16A
 2.39 with sigma of 0.01
 Cl1C-C61C
 1.77 with sigma of 0.02
 Cl2C-Cl1C
 2.916 with sigma of 0.03
 C17A-C15A
 2.39 with sigma of 0.01
 C17-C13
 2.39 with sigma of 0.01
 Cl1B-C61B = C61B-Cl2B
 1.79 with sigma of 0.02
 C18-C16
 2.39 with sigma of 0.01
 Cl1D-C61D = Cl2D-C61D
 1.771 with sigma of 0.01
 Cl2D-C61D
 1.77 with sigma of 0.02
 C17-C15
 2.39 with sigma of 0.01
 Cl1D-Cl2D
 2.916 with sigma of 0.03
 C16-C14
 2.39 with sigma of 0.01
 Cl1D-C61D
 1.78 with sigma of 0.02
 C15-C13
 2.39 with sigma of 0.01
 C14-C18
 2.39 with sigma of 0.01
 C13-C17
 2.39 with sigma of 0.01
 C5-C26A
 1.408 with sigma of 0.0001
 C27-C26A
 1.396 with sigma of 0.0001
 C22-C27
 1.46 with sigma of 0.001
 C62-C19A
 1.4 with sigma of 0.01
 Cl11-Cl10
 2.92 with sigma of 0.04
 Cl1A-Cl2A
 2.92 with sigma of 0.04
 Cl2B-Cl1B
 2.92 with sigma of 0.04
 Cl2C-Cl1C
 2.92 with sigma of 0.04
 Cl1B-Cl2B
 2.929 with sigma of 0.04
 Cl1D-Cl2D
 2.92 with sigma of 0.04
 C20-C19A \\sim C20-C19
 with sigma of 0.02
 C28-C19A \\sim C28-C19
 with sigma of 0.02
 C12A-C11 \\sim C12-C11
 with sigma of 0.02
 C5-C26A \\sim C5-C26
 with sigma of 0.02
 C27-C26 \\sim C27-C26A
 with sigma of 0.02
3. Restrained planarity
 C14A, C15A, C16A, C17A, C22, C23, C24, C25, C26, C27
 with sigma of 0.1
 C11, C12, C13, C14, C15, C16, C17, C18, C19, C20
 with sigma of 0.1
 C25, C16A, C15A, C24, C17A, C14A, C26A, C23A, C22, C27, C5
 with sigma of 0.1
 C64, C26, C27, C22, C23, C24A, C5
 with sigma of 0.1
4. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
Cl10 \\sim Cl11 \\sim C61: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Cl1A \\sim Cl2A \\sim C61A: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Cl1B \\sim Cl2B \\sim C61B: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Cl1C \\sim Cl2C \\sim C61C: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Cl1D \\sim Cl2D \\sim C61D: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
Uanis(C61C) \\sim Ueq, Uanis(Cl2C) \\sim Ueq, Uanis(Cl1C) \\sim Ueq,
Uanis(Cl10) \\sim Ueq, Uanis(Cl11) \\sim Ueq, Uanis(C61) \\sim Ueq, Uanis(Cl1B)
\\sim Ueq, Uanis(Cl2B) \\sim Ueq, Uanis(C61B) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C12A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
6. Rigid body (RIGU) restrains
 C24, C14A, C15A, C16A, C17A, C25, C23, C22, C27, C26
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 Cl10, Cl11, C61
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl1A, Cl2A, C61A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl1B, Cl2B, C61B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl1C, Cl2C, C61C
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 Cl1D, Cl2D, C61D
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
7. Others
 1*[Sof(Cl10)+Sof(Cl11)+Sof(C61)+Sof(H61I)+Sof(H61J)]+1*[Sof(Cl1A)+Sof(Cl2A)+
 Sof(C61A)+Sof(H61A)+Sof(H61B)]+1*[Sof(Cl1B)+Sof(Cl2B)+Sof(C61B)+Sof(H61C)+
 Sof(H61D)]+1*[Sof(Cl1C)+Sof(Cl2C)+Sof(C61C)+Sof(H61E)+Sof(H61F)]+1*[Sof(Cl1D)+
 Sof(Cl2D)+Sof(C61D)+Sof(H61G)+Sof(H61H)]=0.8 with esd of 0.0001
 Sof(C24)=Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(H15A)=Sof(C16A)=Sof(H16A)=
 Sof(C17A)=Sof(H17A)=Sof(C25)=Sof(C62)=Sof(H62)=Sof(C63)=Sof(H63)=Sof(C12A)=
 Sof(H12A)=Sof(C19A)=Sof(C23A)=Sof(H23A)=Sof(C26A)=1-FVAR(1)
 Sof(C12)=Sof(H12)=Sof(C13)=Sof(C14)=Sof(H14)=Sof(C15)=Sof(H15)=Sof(C16)=
 Sof(H16)=Sof(C17)=Sof(H17)=Sof(C18)=Sof(C19)=Sof(C23)=Sof(H23)=Sof(C26)=
 Sof(C64)=Sof(H64)=Sof(C24A)=Sof(H24A)=FVAR(1)
 Sof(Cl10)=Sof(Cl11)=Sof(C61)=Sof(H61I)=Sof(H61J)=FVAR(2)
 Sof(Cl1A)=Sof(Cl2A)=Sof(C61A)=Sof(H61A)=Sof(H61B)=FVAR(3)
 Sof(Cl1B)=Sof(Cl2B)=Sof(C61B)=Sof(H61C)=Sof(H61D)=FVAR(4)
 Sof(Cl1C)=Sof(Cl2C)=Sof(C61C)=Sof(H61E)=Sof(H61F)=FVAR(5)
 Sof(Cl1D)=Sof(Cl2D)=Sof(C61D)=Sof(H61G)=Sof(H61H)=FVAR(6)
8.a Riding coordinates:
 C60(H60A,H60B,H60C)
8.b Secondary CH2 refined with riding coordinates:
 C61A(H61A,H61B), C61B(H61C,H61D), C61C(H61E,H61F), C61D(H61G,H61H), C61(H61I,
 H61J), C37(H37A,H37B), C38(H38A,H38B), C39(H39A,H39B), C49(H49A,H49B),
 C50(H50A,H50B), C51(H51A,H51B)
8.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C6(H6), C7(H7), C12(H12), C15(H15), C23(H23), C14A(H14A), C15A(H15A),
 C16A(H16A), C17A(H17A), C29(H29), C30(H30), C35(H35), C42(H42), C44(H44),
 C46(H46), C54(H54), C56(H56), C58(H58), C64(H64), C62(H62), C63(H63),
 C24A(H24A), C12A(H12A), C23A(H23A)
8.d Idealised Me refined as rotating group:
 C40(H40A,H40B,H40C), C47(H47A,H47B,H47C), C48(H48A,H48B,H48C), C52(H52A,H52B,
 H52C), C59(H59A,H59B,H59C)
;
_shelx_res_checksum              80602
_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 1.482
_oxdiff_exptl_absorpt_empirical_full_min 0.733