π-Bridge Engineering Strategy: Tailoring S-Xanthene Dyes with Strong Absorption for High-Efficiency Photothermal Therapy
Zhao, Yu; Zhang, Rui-Rui; Wang, Nan; Tian, Xiao-Li; Zhang, Li-Na; Xia, Wen-Li; Wang, Zhouyu; Yu, Xiao-Qi; Li, Kun; Materials Horizons  (2025) –; doi:10.1039/D5MH01254F

data_1575580
_publ_section_title
;
 \p-Bridge Engineering Strategy: Tailoring S-Xanthene Dyes with Strong
 Absorption for High-Efficiency Photothermal Therapy
;
_journal_name_full               'Materials Horizons'
_journal_paper_doi               10.1039/D5MH01254F
_journal_year                    2025
_chemical_formula_moiety         'C53 H39 N2 O4 S'
_chemical_formula_sum            'C53 H39 N2 O4 S'
_chemical_formula_weight         799.92
_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             2024-11-05
_audit_creation_method
;
Olex2 1.5-beta
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-02-20 deposited with the CCDC.	2025-08-20 downloaded from the CCDC.
;
_cell_angle_alpha                76.085(3)
_cell_angle_beta                 77.777(2)
_cell_angle_gamma                83.380(2)
_cell_formula_units_Z            2
_cell_length_a                   9.2833(2)
_cell_length_b                   12.8771(4)
_cell_length_c                   20.7969(7)
_cell_measurement_reflns_used    11697
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.4370
_cell_measurement_theta_min      3.5580
_cell_volume                     2353.01(12)
_computing_cell_refinement       'CrysAlisPro 1.171.43.127a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.127a 64-bit (release 16-06-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.127a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-beta (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-beta (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      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_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     40.00  68.00   0.50    0.20    --  106.77 -61.00-180.00   56
  2  \w     58.00  95.00   0.50    0.20    --  106.77 -77.00 -90.00   74
  3  \w     63.00  89.00   0.50    0.20    --  106.77 -77.00  60.00   52
  4  \w     34.00  59.00   0.50    0.20    --  106.77 -61.00 120.00   50
  5  \w     37.00  63.00   0.50    0.20    --  106.77 -61.00 150.00   52
  6  \w     75.00 122.00   0.50    0.20    --  106.77-141.00 109.00   94
  7  \w     34.00  98.00   0.50    0.20    --  106.77 -95.00 120.00  128
  8  \w     47.00  90.00   0.50    0.20    --  106.77 -95.00 -30.00   86
  9  \w     36.00 115.00   0.50    0.20    --  106.77-129.00 -77.00  158
 10  \w     48.00 112.00   0.50    0.20    --  106.77-125.00 -60.00  128
 11  \w     65.00  99.00   0.50    0.20    --  106.77 -95.00 -90.00   68
 12  \w     23.00  48.00   0.50    0.05    --   46.54-129.00 -77.00   50
 13  \w     51.00  93.00   0.50    0.05    --   46.54-129.00 -77.00   84
 14  \w     65.00  91.00   0.50    0.05    --   46.54-141.00 109.00   52
 15  \w    -54.00 -29.00   0.50    0.20    --  -97.00  45.00-150.00   50
 16  \w    -50.00 -25.00   0.50    0.20    --  -97.00  45.00-120.00   50
 17  \w    -54.00 -29.00   0.50    0.20    --  -97.00  45.00 -30.00   50
 18  \w    -54.00 -29.00   0.50    0.20    --  -97.00  45.00  60.00   50
 19  \w    -53.00 -24.00   0.50    0.20    --  -97.00  45.00 120.00   58
 20  \w   -110.00 -27.00   0.50    0.20    --  -97.00 125.00 150.00  166
 21  \w    -80.00 -48.00   0.50    0.05    --  -46.54 141.00 167.00   64
 22  \w   -113.00 -73.00   0.50    0.20    --  -97.00 141.00 167.00   80
 23  \w    -69.00 -44.00   0.50    0.05    --  -46.54 129.00  -4.00   50
 24  \w   -115.00 -58.00   0.50    0.20    --  -97.00 129.00  -4.00  114
 25  \w    -84.00 -28.00   0.50    0.20    --  -97.00 125.00 -30.00  112
 26  \w   -169.00 -88.00   0.50    0.20    --  -97.00 -95.00 -60.00  162
 27  \w   -122.00 -97.00   0.50    0.20    --  -97.00-125.00-120.00   50
 28  \w   -166.00-137.00   0.50    0.20    --  -97.00-125.00-120.00   58
 29  \w   -131.00 -80.00   0.50    0.20    --  -97.00-129.00 -77.00  102
 30  \w   -118.00 -93.00   0.50    0.05    --  -46.54-141.00 109.00   50
 31  \w   -117.00 -78.00   0.50    0.20    --  -97.00-141.00 109.00   78
 32  \w   -170.00 -73.00   0.50    0.20    --  -97.00 -77.00 150.00  194
 33  \w   -115.00 -86.00   0.50    0.20    --  -97.00 -30.00 -30.00   58
 34  \w   -164.00-119.00   0.50    0.20    --  -97.00 -30.00 -30.00   90
 35  \w   -164.00-139.00   0.50    0.20    --  -97.00 -30.00 -60.00   50
 36  \w   -133.00 -82.00   0.50    0.20    --  -97.00 -30.00 -60.00  102
 37  \w    -26.00  40.00   0.50    0.05    --   46.54 -38.00  30.00  132
 38  \w    -25.00  20.00   0.50    0.05    --   46.54 -19.00  90.00   90
 39  \w    -29.00  19.00   0.50    0.05    --   46.54 -19.00 150.00   96
 40  \w    -28.00  22.00   0.50    0.05    --   46.54 -19.00 -90.00  100
 41  \w    -16.00   9.00   0.50    0.05    --   46.54 -19.00   0.00   50
 42  \w     66.00 119.00   0.50    0.05    --   46.54 141.00 167.00  106
 43  \w     95.00 120.00   0.50    0.20    --  106.77 141.00 167.00   50
 44  \w     57.00 116.00   0.50    0.05    --   46.54  77.00 120.00  118
 45  \w    119.00 167.00   0.50    0.20    --  106.77  45.00 150.00   96
 46  \w     77.00 110.00   0.50    0.20    --  106.77 129.00  -4.00   66
 47  \w    126.00 174.00   0.50    0.20    --  106.77 125.00-150.00   96
 48  \w     87.00 113.00   0.50    0.20    --  106.77 125.00-150.00   52
;
_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      0.0438166000
_diffrn_orient_matrix_UB_12      0.0973384000
_diffrn_orient_matrix_UB_13      -0.0579764000
_diffrn_orient_matrix_UB_21      -0.0109881000
_diffrn_orient_matrix_UB_22      0.0699027000
_diffrn_orient_matrix_UB_23      0.0516757000
_diffrn_orient_matrix_UB_31      0.1640869000
_diffrn_orient_matrix_UB_32      -0.0300060000
_diffrn_orient_matrix_UB_33      0.0035545000
_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  0.0509
_diffrn_reflns_av_unetI/netI     0.0486
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            30094
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        66.595
_diffrn_reflns_theta_max         66.595
_diffrn_reflns_theta_min         3.744
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.962
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.69333
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.127a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light green'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.129
_exptl_crystal_description       block
_exptl_crystal_F_000             838
_exptl_crystal_size_max          0.23
_exptl_crystal_size_mid          0.18
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.492
_refine_diff_density_min         -0.288
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     543
_refine_ls_number_reflns         8249
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0687
_refine_ls_R_factor_gt           0.0573
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0845P)^2^+2.3680P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1577
_refine_ls_wR_factor_ref         0.1648
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6773
_reflns_number_total             8249
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5mh01254f4.cif
_cod_data_source_block           b
_cod_database_code               1575580
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHO
_shelx_estimated_absorpt_t_max   0.910
_shelx_estimated_absorpt_t_min   0.809
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C10(H10), C11(H11),
 C12(H12), C14(H14), C15(H15), C18(H18), C19(H19), C22(H22), C26(H26), C27(H27),
  C28(H28), C33(H33), C34(H34), C36(H36), C39(H39), C40(H40), C43(H43),
 C44(H44), C45(H45), C46(H46), C47(H47), C49(H49), C50(H50), C51(H51), C52(H52),
  C53(H53)
2.b Idealised Me refined as rotating group:
 C30(H30A,H30B,H30C), C31(H31A,H31B,H31C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              26952
_shelx_fab_checksum              12853
_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 1.820
_oxdiff_exptl_absorpt_empirical_full_min 0.729