Valence state engineering in multi-heteroatom-doped PAHs: a strategy for tunable photophysical properties and phototheranostic potentials.
Ma, Yao; Li, Dongxu; Chen, Xin; Hua, Xinqiang; Yuan, Cheng-Shan; Wang, Jianguo; Liu, Zitong; Zhang, Hao-Li; Shao, Xiangfeng; Chemical science 16 (2025) 13057–13069; doi:10.1039/d5sc02061a

data_1574877
_publ_section_title
;
 Valence state engineering in multi-heteroatom-doped PAHs: a strategy for
 tunable photophysical properties and phototheranostic potentials.
;
_journal_issue                   28
_journal_name_full               'Chemical science'
_journal_page_first              13057
_journal_page_last               13069
_journal_paper_doi               10.1039/d5sc02061a
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C84 H94 N2 O20 S4'
_chemical_formula_sum            'C84 H92 N2 O20 S4'
_chemical_formula_weight         1577.83
_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             2024-04-11
_audit_creation_method
;
Olex2 1.5-ac5-024
(compiled 2022.04.12 svn.rca3783a0 for Rigaku Oxford Diffraction, GUI svn.r6498)
;
_audit_update_record
;
2025-02-14 deposited with the CCDC.	2025-06-16 downloaded from the CCDC.
;
_cell_angle_alpha                99.057(2)
_cell_angle_beta                 96.562(2)
_cell_angle_gamma                93.372(2)
_cell_formula_units_Z            3
_cell_length_a                   15.8904(3)
_cell_length_b                   18.3627(6)
_cell_length_c                   20.0324(4)
_cell_measurement_reflns_used    15340
_cell_measurement_temperature    149.99(12)
_cell_measurement_theta_max      75.9130
_cell_measurement_theta_min      2.2700
_cell_volume                     5717.0(2)
_computing_cell_refinement       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.93a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac5-024 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac5-024 (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      149.99(12)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.993
_diffrn_measured_fraction_theta_max 0.940
_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    -74.00 -38.00   0.50    8.00    --  -44.30 109.00 -37.00   72
  2  \w      9.00  85.00   0.50    8.00    --   44.30-109.00-133.00  152
  3  \w   -107.00 -81.00   0.50   17.00    -- -100.00 109.00 -37.00   52
  4  \w   -162.00-130.00   0.50   17.00    -- -100.00-109.00-133.00   64
  5  \w    129.00 154.00   0.50   17.00    --  109.64 109.00 -37.00   50
  6  \w     79.00 107.00   0.50   17.00    --  109.64-109.00-133.00   56
  7  \w    -30.00  35.00   0.50    8.00    --  -44.30  19.00  60.00  130
  8  \w    -30.00  35.00   0.50    8.00    --  -44.30  19.00 120.00  130
  9  \w     43.00 118.00   0.50    8.00    --   44.30 179.00 120.00  150
 10  \w    -12.00  14.00   0.50    8.00    --   44.30 -19.00-150.00   52
 11  \w     17.00 114.00   0.50    8.00    --   44.30  77.00 -30.00  194
 12  \w     50.00 120.00   0.50    8.00    --   44.30-179.00-120.00  140
 13  \w    -95.00 -69.00   0.50   17.00    -- -100.00 125.00 150.00   52
 14  \w    -55.00 -30.00   0.50   17.00    -- -100.00 125.00   0.00   50
 15  \w    -67.00 -41.00   0.50   17.00    -- -100.00 125.00 150.00   52
 16  \w    -54.00 -29.00   0.50   17.00    -- -100.00  45.00 120.00   50
 17  \w   -172.00 -70.00   0.50   17.00    -- -100.00 -15.00 150.00  204
 18  \w    -54.00 -25.00   0.50   17.00    -- -100.00  45.00  90.00   58
 19  \w    -54.00 -28.00   0.50   17.00    -- -100.00  45.00 -60.00   52
 20  \w   -112.00 -29.00   0.50   17.00    -- -100.00 125.00 -60.00  166
 21  \w   -169.00-142.00   0.50   17.00    -- -100.00-125.00-180.00   54
 22  \w   -174.00 -79.00   0.50   17.00    -- -100.00 -45.00  90.00  190
 23  \w   -145.00 -86.00   0.50   17.00    -- -100.00 -45.00 -60.00  118
 24  \w   -135.00 -85.00   0.50   17.00    -- -100.00-125.00-180.00  100
 25  \w    -54.00 -29.00   0.50   17.00    -- -100.00  45.00-180.00   50
 26  \w   -111.00 -31.00   0.50   17.00    -- -100.00 125.00 120.00  160
 27  \w   -132.00 -79.00   0.50   17.00    -- -100.00 154.00 129.58  106
 28  \w   -111.00 -76.00   0.50   17.00    -- -100.00 125.00   0.00   70
 29  \w   -122.00 -63.00   0.50   17.00    -- -100.00 139.00-173.54  118
 30  \w    -72.00 -29.00   0.50   17.00    -- -100.00  61.00 -60.00   86
 31  \w     45.00  99.00   0.50   17.00    --  109.64 -77.00  60.00  108
 32  \w     38.00  95.00   0.50   17.00    --  109.64 -77.00  30.00  114
 33  \w     36.00  61.00   0.50   17.00    --  109.64 -61.00 150.00   50
 34  \w     92.00 174.00   0.50   17.00    --  109.64  45.00-120.00  164
 35  \w     73.00 102.00   0.50   17.00    --  109.64 -94.00 -30.00   58
 36  \w     79.00 106.00   0.50   17.00    --  109.64 -94.00  60.00   54
 37  \w     69.00 108.00   0.50   17.00    --  109.64-125.00 -30.00   78
 38  \w     40.00  77.00   0.50   17.00    --  109.64-125.00-180.00   74
 39  \w     39.00 107.00   0.50   17.00    --  109.64-125.00  60.00  136
 40  \w     43.00  68.00   0.50   17.00    --  109.64 -61.00 -90.00   50
 41  \w     44.00 103.00   0.50   17.00    --  109.64 -77.00-180.00  118
 42  \w     78.00 128.00   0.50   17.00    --  109.64  15.00  30.00  100
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0032676000
_diffrn_orient_matrix_UB_12      0.0822497000
_diffrn_orient_matrix_UB_13      -0.0067183000
_diffrn_orient_matrix_UB_21      -0.0093201000
_diffrn_orient_matrix_UB_22      0.0192290000
_diffrn_orient_matrix_UB_23      0.0763419000
_diffrn_orient_matrix_UB_31      0.0973889000
_diffrn_orient_matrix_UB_32      0.0113011000
_diffrn_orient_matrix_UB_33      0.0169657000
_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  0.1004
_diffrn_reflns_av_unetI/netI     0.0944
_diffrn_reflns_Laue_measured_fraction_full 0.993
_diffrn_reflns_Laue_measured_fraction_max 0.940
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            71860
_diffrn_reflns_point_group_measured_fraction_full 0.993
_diffrn_reflns_point_group_measured_fraction_max 0.940
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.570
_diffrn_reflns_theta_min         2.251
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.780
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.60399
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.93a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light red'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.375
_exptl_crystal_description       needle
_exptl_crystal_F_000             2502
_exptl_crystal_size_max          0.12
_exptl_crystal_size_mid          0.05
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.889
_refine_diff_density_min         -0.696
_refine_diff_density_rms         0.082
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.001
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1501
_refine_ls_number_reflns         22597
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.001
_refine_ls_R_factor_all          0.1209
_refine_ls_R_factor_gt           0.0711
_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^)+(0.1233P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1859
_refine_ls_wR_factor_ref         0.2189
_reflns_Friedel_coverage         0.000
_reflns_number_gt                13165
_reflns_number_total             22597
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02061a2.cif
_cod_data_source_block           mayao_0410_auto
_cod_depositor_comments
'Adding full bibliography for 1574877--1574879.cif.'
_cod_database_code               1574877
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C19(H19A,H19B), C23(H23A,H23B), C27(H27A,H27B), C30(H30A,H30B), C32(H32A,
 H32B), C35(H35A,H35B), C42(H42A,H42B), C44(H44A,H44B), C47(H47A,H47B),
 C52(H52A,H52B), C60(H60A,H60B), C63(H63A,H63B), C81(H81A,H81B), C93(H93A,H93B),
  C99(H99A,H99B), C120(H12A,H12B), C130(H13A,H13B), C133(H13C,H13D), C138(H13E,
 H13F), C143(H14A,H14B), C144(H14C,H14D), C153(H15A,H15B), C156(H15C,H15D),
 C158(H15E,H15F), C167(H16D,H16E), C168(H16F,H16G), C171(H17A,H17B), C180(H18A,
 H18B), C183(H18C,H18D), C189(H18E,H18F), C220(H22A,H22B), C225(H22C,H22D),
 C230(H23C,H23D), C231(H23E,H23F), C233(H23G,H23H), C234(H23I,H23J), C242(H24A,
 H24B), C245(H24C,H24D), C251(H25A,H25B), C254(H25C,H25D), C261(H26A,H26B),
 C265(H26C,H26D), C276(H27F,H27G), C287(H28A,H28B), C297(H29A,H29B)
2.b Aromatic/amide H refined with riding coordinates:
 N26(H26), N106(H106), C69(H69), C82(H82), N227(H227), C283(H283)
2.c Idealised Me refined as rotating group:
 C58(H58A,H58B,H58C), C66(H66A,H66B,H66C), C73(H73A,H73B,H73C), C77(H77A,H77B,
 H77C), C104(H10A,H10B,H10C), C148(H14E,H14F,H14G), C164(H16A,H16B,H16C),
 C177(H17C,H17D,H17E), C192(H19C,H19D,H19E), C195(H19F,H19G,H19H), C258(H25E,
 H25F,H25G), C268(H26E,H26F,H26G), C275(H27C,H27D,H27E), C279(H27H,H27I,H27J),
 C300(H30C,H30D,H30E)
;
_shelx_res_checksum              96235
_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 2.953
_oxdiff_exptl_absorpt_empirical_full_min 0.289