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_1574879
_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         'C46 H52 N O6 S2, C F3 O3 S'
_chemical_formula_sum            'C47 H52 F3 N O9 S3'
_chemical_formula_weight         928.07
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-06-25
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2019.04.23 svn.r3594 for Rigaku Oxford Diffraction, GUI svn.r5739)
;
_audit_update_record
;
2025-02-14 deposited with the CCDC.	2025-06-16 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.0850(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.10600(10)
_cell_length_b                   18.7587(2)
_cell_length_c                   25.8895(2)
_cell_measurement_reflns_used    19051
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      77.4450
_cell_measurement_theta_min      2.8970
_cell_volume                     4415.95(8)
_computing_cell_refinement       'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.103a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      149.99(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.947
_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    -80.00 -55.00   0.50    0.89    --  -47.57 119.00 130.00   50
  2  \w    -90.00 -65.00   0.50    0.89    --  -47.57-156.00-110.00   50
  3  \w     27.00  91.00   0.50    0.89    --   47.57-119.00  45.00  128
  4  \w     49.00  74.00   0.50    0.89    --   47.57-156.00-110.00   50
  5  \w     58.00  84.00   0.50    0.89    --   47.57 156.00 -73.00   52
  6  \w   -109.00 -84.00   0.50    3.00    -- -100.00 156.00 -73.00   50
  7  \w   -154.00-129.00   0.50    3.00    -- -100.00-119.00  45.00   50
  8  \w   -135.00-110.00   0.50    3.00    -- -100.00-156.00-110.00   50
  9  \w   -109.00 -67.00   0.50    3.00    -- -100.00 119.00 130.00   84
 10  \w     74.00 109.00   0.50    3.00    --  107.75-119.00  45.00   70
 11  \w     55.00 155.00   0.50    3.00    --  107.75 156.00 -73.00  200
 12  \w     60.00  85.00   0.50    3.00    --  107.75-156.00-110.00   50
 13  \w    103.00 137.00   0.50    3.00    --  107.75 119.00 130.00   68
 14  \w    -27.00  28.00   0.50    0.89    --  -47.57  19.00 -90.00  110
 15  \w    -19.00  20.00   0.50    0.89    --   47.57 -19.00 120.00   78
 16  \w    -27.00  23.00   0.50    0.89    --   47.57 -19.00-150.00  100
 17  \w    -11.00  17.00   0.50    0.89    --   47.57 -19.00-120.00   56
 18  \w   -154.00 -88.00   0.50    3.00    -- -100.00 -19.00  60.00  132
 19  \w    -69.00 -29.00   0.50    3.00    -- -100.00  57.00 -60.00   80
 20  \w   -173.00-101.00   0.50    3.00    -- -100.00 -37.00-120.00  144
 21  \w   -111.00 -31.00   0.50    3.00    -- -100.00 125.00 -90.00  160
 22  \w    132.00 175.00   0.50    3.00    --  107.75  57.00   0.00   86
 23  \w     40.00 112.00   0.50    3.00    --  107.75-125.00-120.00  144
 24  \w     35.00  60.00   0.50    3.00    --  107.75 -57.00  90.00   50
 25  \w     39.00 100.00   0.50    3.00    --  107.75 -77.00  60.00  122
 26  \w     63.00  93.00   0.50    3.00    --  107.75 -77.00   0.00   60
 27  \w     35.00  60.00   0.50    3.00    --  107.75 -77.00  30.00   50
 28  \w     35.00  60.00   0.50    3.00    --  107.75 -57.00-150.00   50
 29  \w     38.00  63.00   0.50    3.00    --  107.75 -57.00-180.00   50
;
_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      -0.0124374000
_diffrn_orient_matrix_UB_12      0.0032612000
_diffrn_orient_matrix_UB_13      0.0590513000
_diffrn_orient_matrix_UB_21      -0.0210212000
_diffrn_orient_matrix_UB_22      0.0814105000
_diffrn_orient_matrix_UB_23      -0.0032682000
_diffrn_orient_matrix_UB_31      -0.1676490000
_diffrn_orient_matrix_UB_32      -0.0105032000
_diffrn_orient_matrix_UB_33      -0.0071643000
_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  0.0335
_diffrn_reflns_av_unetI/netI     0.0282
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.947
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            35941
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.947
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.841
_diffrn_reflns_theta_min         2.911
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.135
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.58068
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.103a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark blue'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.396
_exptl_crystal_description       needle
_exptl_crystal_F_000             1952
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.03
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.848
_refine_diff_density_min         -0.634
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.017
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     574
_refine_ls_number_reflns         8940
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.017
_refine_ls_R_factor_all          0.0592
_refine_ls_R_factor_gt           0.0502
_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^)+(0.0701P)^2^+4.2446P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1327
_refine_ls_wR_factor_ref         0.1386
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7562
_reflns_number_total             8940
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02061a2.cif
_cod_data_source_block           mayao_0624_auto
_cod_depositor_comments
'Adding full bibliography for 1574877--1574879.cif.'
_cod_database_code               1574879
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.96
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_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.a Secondary CH2 refined with riding coordinates:
 C015(H01D,H01E), C016(H01F,H01G), C017(H01H,H01I), C01A(H01J,H01K), C01B(H01L,
 H01M), C01C(H01N,H01O), C01D(H01P,H01Q), C01E(H01R,H01S), C01F(H01T,H01U),
 C01G(H01V,H01W), C01H(H01X,H01Y), C01J(H01,HB), C01K(H1,HC), C01L(H2,HD),
 C01M(H3,HE)
2.b Aromatic/amide H refined with riding coordinates:
 C00Y(H00Y), C011(H011), C012(H012), C019(H019)
2.c Idealised Me refined as rotating group:
 C014(H01A,H01B,H01C), C01I(H01Z,H,HA), C01O(H4,HF,HG), C01P(H5,HH,HI),
 C01Q(H6,HJ,HK), C01R(H7,HL,HM)
;
_shelx_res_checksum              23833
_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 1.571
_oxdiff_exptl_absorpt_empirical_full_min 0.642