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_1575581
_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         'C55 H39 O2 S3, 1.5(Cl), 3[CH2Cl2]'
_chemical_formula_sum            'C106 H78 Cl3 N4 O4 S6'
_chemical_formula_weight         1770.43
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-11-08
_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                90
_cell_angle_beta                 95.547(2)
_cell_angle_gamma                90
_cell_formula_units_Z            1
_cell_length_a                   7.3793(2)
_cell_length_b                   25.8344(5)
_cell_length_c                   13.6816(3)
_cell_measurement_reflns_used    27531
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      75.2740
_cell_measurement_theta_min      3.3870
_cell_volume                     2596.04(10)
_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      100.00(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 0.996
_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     41.00  92.00   0.50    0.20    --  108.10 -77.00-180.00  102
  2  \w     38.00  99.00   0.50    0.20    --  108.10 -77.00-150.00  122
  3  \w     36.00  62.00   0.50    0.20    --  108.10 -61.00 -30.00   52
  4  \w     38.00  63.00   0.50    0.20    --  108.10 -61.00   0.00   50
  5  \w     34.00  61.00   0.50    0.20    --  108.10 -61.00  60.00   54
  6  \w     34.00  59.00   0.50    0.20    --  108.10 -61.00-180.00   50
  7  \w      6.00  45.00   0.50    0.05    --   42.46-108.00-170.00   78
  8  \w     53.00 108.00   0.50    0.20    --  108.10-108.00-170.00  110
  9  \w    -36.00  23.00   0.50    0.05    --   42.46 -19.00   0.00  118
 10  \w    -35.00  10.00   0.50    0.05    --   42.46 -19.00  90.00   90
 11  \w    -22.00  22.00   0.50    0.05    --   42.46 -19.00 120.00   88
 12  \w     85.00 143.00   0.50    0.20    --  108.10 108.00 -73.00  116
 13  \w    -46.00  28.00   0.50    0.05    --  -42.46  38.00-120.00  148
 14  \w   -105.00 -49.00   0.50    0.20    --  -97.00 108.00 -73.00  112
 15  \w    -63.00 -13.00   0.50    0.05    --  -42.46 108.00 -73.00  100
 16  \w   -149.00-102.00   0.50    0.20    --  -97.00-108.00-170.00   94
 17  \w   -109.00 -82.00   0.50    0.20    --  -97.00-125.00 150.00   54
 18  \w   -156.00-114.00   0.50    0.20    --  -97.00-125.00 150.00   84
 19  \w    -73.00 -38.00   0.50    0.20    --  -97.00  61.00  90.00   70
 20  \w    -54.00 -27.00   0.50    0.20    --  -97.00  61.00 150.00   54
 21  \w    -53.00 -21.00   0.50    0.20    --  -97.00  45.00  60.00   64
 22  \w    -54.00 -21.00   0.50    0.20    --  -97.00  45.00  90.00   66
 23  \w    -52.00 -21.00   0.50    0.20    --  -97.00  45.00  30.00   62
 24  \w    -54.00 -27.00   0.50    0.20    --  -97.00  45.00-150.00   54
 25  \w    -54.00 -21.00   0.50    0.20    --  -97.00  45.00 -90.00   66
 26  \w    -66.00 -24.00   0.50    0.20    --  -97.00  61.00 -60.00   84
 27  \w    -54.00 -21.00   0.50    0.20    --  -97.00  45.00 120.00   66
 28  \w    -53.00 -23.00   0.50    0.20    --  -97.00  45.00 150.00   60
 29  \w    -12.00  14.00   0.50    0.05    --   42.76 -19.00 -90.00   52
 30  \w    -29.00  39.00   0.50    0.05    --   42.76 -38.00  60.00  136
 31  \w     15.00  40.00   0.50    0.05    --   42.76 -38.00-180.00   50
 32  \w     43.00  76.00   0.50    0.05    --   42.76 -99.00  60.00   66
 33  \w    -34.00   2.00   0.50    0.05    --   42.76 -38.00-180.00   72
 34  \w      4.00  36.00   0.50    0.05    --   42.76 -99.00  60.00   64
 35  \w   -173.00-148.00   0.50    0.20    --  -97.00 -30.00 150.00   50
 36  \w   -163.00-122.00   0.50    0.20    --  -97.00 -63.00  84.08   82
 37  \w    -48.00 -23.00   0.50    0.20    --  -97.00  45.00-180.00   50
 38  \w   -171.00-107.00   0.50    0.20    --  -97.00 -55.00 105.60  128
 39  \w   -112.00 -81.00   0.50    0.20    --  -97.00 -30.00 150.00   62
 40  \w    -65.00 -34.00   0.50    0.20    --  -97.00 148.00 -74.67   62
 41  \w    -50.00 -25.00   0.50    0.20    --  -97.00 125.00 -60.00   50
 42  \w   -102.00 -74.00   0.50    0.20    --  -97.00 125.00 -60.00   56
 43  \w    -99.00 -74.00   0.50    0.20    --  -97.00 -63.00  84.08   50
 44  \w   -128.00 -72.00   0.50    0.20    --  -97.00 148.00 -74.67  112
 45  \w   -167.00-123.00   0.50    0.20    --  -97.00 -48.00  52.42   88
 46  \w     71.00 105.00   0.50    0.20    --  107.55 -95.00 -30.00   68
 47  \w     63.00  91.00   0.50    0.20    --  107.55 -95.00  60.00   56
 48  \w     82.00 111.00   0.50    0.20    --  107.55-125.00 120.00   58
 49  \w    137.00 172.00   0.50    0.20    --  107.55  45.00 -30.00   70
 50  \w     90.00 116.00   0.50    0.20    --  107.55  45.00 -30.00   52
 51  \w     86.00 111.00   0.50    0.20    --  107.55-125.00 -60.00   50
 52  \w     35.00  66.00   0.50    0.20    --  107.55 -61.00 -90.00   62
 53  \w     54.00  80.00   0.50    0.20    --  107.55-125.00 -60.00   52
 54  \w     52.00 110.00   0.50    0.20    --  107.55-125.00-180.00  116
 55  \w     46.00  90.00   0.50    0.20    --  107.55 -77.00   0.00   88
 56  \w     61.00 111.00   0.50    0.20    --  107.55-125.00 150.00  100
 57  \w   -117.00 -19.00   0.50    0.05    --  -42.76 -65.00 -93.46  196
 58  \w   -117.00 -20.00   0.50    0.05    --  -42.76 -57.00-180.00  194
 59  \w   -117.00 -19.00   0.50    0.05    --  -42.76 -64.00 -58.70  196
 60  \w   -117.00 -20.00   0.50    0.05    --  -42.76 -57.00  60.00  194
 61  \w   -117.00 -14.00   0.50    0.05    --  -42.76 -77.00  30.00  206
 62  \w   -117.00 -16.00   0.50    0.05    --  -42.76 -72.00 143.92  202
 63  \w     14.00 117.00   0.50    0.05    --   42.76  77.00-180.00  206
 64  \w     14.00 117.00   0.50    0.05    --   42.76  77.00 -30.00  206
 65  \w     21.00 120.00   0.50    0.05    --   42.76  38.00 -60.00  198
 66  \w     17.00  95.00   0.50    0.05    --   42.76-125.00  90.00  156
 67  \w     14.00 117.00   0.50    0.05    --   42.76  77.00  90.00  206
 68  \w   -174.00-107.00   0.50    0.20    --  -97.00 -30.00-120.00  134
;
_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      0.1125914000
_diffrn_orient_matrix_UB_12      0.0308538000
_diffrn_orient_matrix_UB_13      -0.0691667000
_diffrn_orient_matrix_UB_21      -0.1094113000
_diffrn_orient_matrix_UB_22      0.0491922000
_diffrn_orient_matrix_UB_23      0.0190920000
_diffrn_orient_matrix_UB_31      0.1390392000
_diffrn_orient_matrix_UB_32      0.0137163000
_diffrn_orient_matrix_UB_33      0.0873993000
_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  0.0878
_diffrn_reflns_av_unetI/netI     0.0473
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -30
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            40183
_diffrn_reflns_point_group_measured_fraction_full 0.988
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.057
_diffrn_reflns_theta_max         67.057
_diffrn_reflns_theta_min         3.669
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.312
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.40676
_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    1.132
_exptl_crystal_description       block
_exptl_crystal_F_000             921
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.928
_refine_diff_density_min         -0.512
_refine_diff_density_rms         0.109
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.26(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.297
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     477
_refine_ls_number_reflns         9160
_refine_ls_number_restraints     349
_refine_ls_restrained_S_all      1.296
_refine_ls_R_factor_all          0.1016
_refine_ls_R_factor_gt           0.0991
_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^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2749
_refine_ls_wR_factor_ref         0.2794
_reflns_Friedel_coverage         0.937
_reflns_Friedel_fraction_full    0.980
_reflns_Friedel_fraction_max     0.980
_reflns_number_gt                8706
_reflns_number_total             9160
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5mh01254f4.cif
_cod_data_source_block           sx-thio-dpa
_cod_database_code               1575581
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         CHSO
_shelx_estimated_absorpt_t_max   0.802
_shelx_estimated_absorpt_t_min   0.802
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.74(3)
 0.26(3)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 C44-N2
 1.45 with sigma of 0.02
 N2-C50
 1.45 with sigma of 0.02
 N2-C43
 1.45 with sigma of 0.02
 C43-C42
 1.45 with sigma of 0.02
 C42-C41
 1.45 with sigma of 0.02
 C41-C40
 1.45 with sigma of 0.02
 C40-C37
 1.45 with sigma of 0.02
 C25-C22 = C25-C26 = C25-C34
 1.45 with sigma of 0.02
 C25-C26
 1.45 with sigma of 0.02
 C18-C19
 1.45 with sigma of 0.02
 C17-C18
 1.45 with sigma of 0.02
 C17-C16
 1.45 with sigma of 0.02
 C16-C15
 1.45 with sigma of 0.02
 C15-N1
 1.45 with sigma of 0.02
 N1-C3
 1.45 with sigma of 0.02
 N1-C9
 1.45 with sigma of 0.02
4. Rigid bond restraints
 C29, C30
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
5. Uiso/Uaniso restraints and constraints
Uanis(N2) \\sim Ueq, Uanis(N1) \\sim Ueq, Uanis(C40) \\sim Ueq, Uanis(C10)
\\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(C37) \\sim Ueq,
Uanis(C34) \\sim Ueq, Uanis(C44) \\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C25)
\\sim Ueq, Uanis(C50) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C22) \\sim Ueq,
Uanis(C36) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C38)
\\sim Ueq, Uanis(C47) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C41) \\sim Ueq,
Uanis(C51) \\sim Ueq, Uanis(C26) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C17)
\\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C27) \\sim Ueq,
Uanis(C19) \\sim Ueq, Uanis(C52) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C49)
\\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C31) \\sim Ueq,
Uanis(C12) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C16)
\\sim Ueq, Uanis(C18) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C5) \\sim Ueq,
Uanis(C53) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C48)
\\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C33) \\sim Ueq, Uanis(C30) \\sim Ueq,
Uanis(C55) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C7) \\sim
Ueq, Uanis(C54) \\sim Ueq, Uanis(C29) \\sim Ueq: with sigma of 0.01 and sigma
for terminal atoms of 0.02
6. Others
 Fixed Sof: Cl2(0.5)
 Fixed Y: S1(0.405869)
7.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C6(H6), C7(H7), C8(H8), C14(H14), C10(H10), C11(H11),
 C12(H12), C13(H13), C16(H16), C17(H17), C20(H20), C21(H21), C24(H24), C31(H31),
  C30(H30), C29(H29), C36(H36), C39(H39), C38(H38), C41(H41), C42(H42),
 C48(H48), C47(H47), C46(H46), C45(H45), C49(H49), C55(H55), C51(H51), C52(H52),
  C53(H53), C54(H54)
7.b Fitted hexagon refined as free rotating group:
 C4(C5,C6,C7,C8,C3), C14(C9,C10,C11,C12,C13), C20(C21,C22,C23,C24,C19),
 C27(C26,C32,C31,C30,C29), C36(C35,C34,C39,C38,C37), C48(C47,C46,C45,C44,C49),
 C55(C50,C51,C52,C53,C54)
7.c Idealised Me refined as rotating group:
 C28(H28A,H28B,H28C), C33(H33A,H33B,H33C)
;
_smtbx_masks_void_probe_radius   0.1
_smtbx_masks_void_truncation_radius 0.1
_shelx_res_checksum              25982
_shelx_fab_checksum              19310
_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 2.325
_oxdiff_exptl_absorpt_empirical_full_min 0.534