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_1574878
_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 Se2, C F3 O3 S'
_chemical_formula_sum            'C47 H52 F3 N O9 S Se2'
_chemical_formula_weight         1021.87
_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             2021-07-02
_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                 92.9385(14)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.12078(14)
_cell_length_b                   18.7864(3)
_cell_length_c                   25.9913(4)
_cell_measurement_reflns_used    20592
_cell_measurement_temperature    149.99(10)
_cell_measurement_theta_max      76.7420
_cell_measurement_theta_min      2.8950
_cell_volume                     4447.67(12)
_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 0.996
_diffrn_measured_fraction_theta_max 0.941
_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   -119.00 -68.00   0.50    0.80    --  -47.57-145.00 -55.00  102
  2  \w    -61.00 -34.00   0.50    0.80    --  -47.57 125.00-170.00   54
  3  \w    -98.00 -64.00   0.50    0.80    --  -47.57 145.00  -3.00   68
  4  \w     62.00 113.00   0.50    0.80    --   47.57 145.00  -3.00  102
  5  \w    -94.00 -69.00   0.50    3.00    -- -100.00 125.00-170.00   50
  6  \w   -152.00-127.00   0.50    3.00    -- -100.00-125.00 111.00   50
  7  \w   -125.00 -34.00   0.50    3.00    -- -100.00 145.00  -3.00  182
  8  \w     82.00 120.00   0.50    3.00    --  107.75 125.00-170.00   76
  9  \w     49.00  74.00   0.50    3.00    --  107.75-125.00 111.00   50
 10  \w     81.00 122.00   0.50    3.00    --  107.75-145.00 -55.00   82
 11  \w     35.00  66.00   0.50    3.00    --  107.75-145.00 -55.00   62
 12  \w    -26.00  21.00   0.50    0.80    --   47.57 -19.00  90.00   94
 13  \w    -23.00  23.00   0.50    0.80    --   47.57 -19.00-150.00   92
 14  \w    -13.00  22.00   0.50    0.80    --   47.57 -19.00 -60.00   70
 15  \w    -26.00  11.00   0.50    0.80    --   47.57 -19.00-180.00   74
 16  \w    -27.00  -2.00   0.50    0.80    --   47.57 -19.00   0.00   50
 17  \w   -121.00 -93.00   0.50    3.00    -- -100.00 -37.00 -60.00   56
 18  \w   -111.00 -27.00   0.50    3.00    -- -100.00 125.00 150.00  168
 19  \w   -143.00-118.00   0.50    3.00    -- -100.00-145.00 -55.00   50
 20  \w   -123.00 -90.00   0.50    3.00    -- -100.00 141.00  95.49   66
 21  \w    -77.00 -42.00   0.50    3.00    -- -100.00 141.00  95.49   70
 22  \w    -66.00 -27.00   0.50    3.00    -- -100.00  57.00-120.00   78
 23  \w   -159.00 -86.00   0.50    3.00    -- -100.00 -57.00  30.00  146
 24  \w   -169.00 -82.00   0.50    3.00    -- -100.00-125.00 -90.00  174
 25  \w     37.00  62.00   0.50    3.00    --  107.75 -57.00-120.00   50
 26  \w     35.00  60.00   0.50    3.00    --  107.75 -57.00 150.00   50
 27  \w    126.00 175.00   0.50    3.00    --  107.75  19.00 120.00   98
 28  \w     35.00  86.00   0.50    3.00    --  107.75 -77.00 120.00  102
 29  \w     46.00  90.00   0.50    3.00    --  107.75 -99.00 120.00   88
;
_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      -0.0604865000
_diffrn_orient_matrix_UB_12      0.0707724000
_diffrn_orient_matrix_UB_13      -0.0222526000
_diffrn_orient_matrix_UB_21      -0.1190798000
_diffrn_orient_matrix_UB_22      -0.0410699000
_diffrn_orient_matrix_UB_23      -0.0319864000
_diffrn_orient_matrix_UB_31      -0.1037260000
_diffrn_orient_matrix_UB_32      0.0058624000
_diffrn_orient_matrix_UB_33      0.0447472000
_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  0.0536
_diffrn_reflns_av_unetI/netI     0.0374
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.941
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       32
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            35285
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.941
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.768
_diffrn_reflns_theta_min         2.904
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.115
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.54570
_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 brown'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.526
_exptl_crystal_description       needle
_exptl_crystal_F_000             2096
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.304
_refine_diff_density_min         -0.999
_refine_diff_density_rms         0.128
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.171
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     574
_refine_ls_number_reflns         8931
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.171
_refine_ls_R_factor_all          0.0847
_refine_ls_R_factor_gt           0.0767
_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^)+(0.0428P)^2^+38.7171P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1918
_refine_ls_wR_factor_ref         0.1948
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7998
_reflns_number_total             8931
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc02061a2.cif
_cod_data_source_block           mayao-sech3_0702-3_auto
_cod_depositor_comments
'Adding full bibliography for 1574877--1574879.cif.'
_cod_original_cell_volume        4447.66(12)
_cod_database_code               1574878
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 99.95
_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:
 C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B), C30(H30A,H30B), C31(H31A,
 H31B), C32(H32A,H32B), C34(H34A,H34B), C35(H35A,H35B), C36(H36A,H36B),
 C38(H38A,H38B), C39(H39A,H39B), C40(H40A,H40B), C43(H43A,H43B), C44(H44A,H44B),
  C45(H45A,H45B)
2.b Aromatic/amide H refined with riding coordinates:
 C21(H21), C22(H22), C23(H23), C24(H24)
2.c Idealised Me refined as rotating group:
 C29(H29A,H29B,H29C), C33(H33A,H33B,H33C), C37(H37A,H37B,H37C), C41(H41A,H41B,
 H41C), C42(H42A,H42B,H42C), C46(H46A,H46B,H46C)
;
_shelx_res_checksum              20740
_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 1.952
_oxdiff_exptl_absorpt_empirical_full_min 0.277