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_1575582
_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         'C57 H43 N2 O2 S'
_chemical_formula_sum            'C57 H43 N2 O2 S'
_chemical_formula_weight         819.99
_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             2025-04-24
_audit_creation_method
;
Olex2 1.5
(compiled 2025.04.05 svn.rf049d14d for OlexSys, GUI svn.r7221)
;
_audit_update_record
;
2025-04-25 deposited with the CCDC.	2025-08-20 downloaded from the CCDC.
;
_cell_angle_alpha                102.0310(10)
_cell_angle_beta                 92.1560(10)
_cell_angle_gamma                108.3260(10)
_cell_formula_units_Z            4
_cell_length_a                   13.0788(2)
_cell_length_b                   16.7275(2)
_cell_length_c                   23.7123(3)
_cell_measurement_reflns_used    42025
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      55.2120
_cell_measurement_theta_min      3.1040
_cell_volume                     4786.58(12)
_computing_cell_refinement       'CrysAlisPro 1.171.43.116a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.116a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.116a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (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 0.998
_diffrn_measured_fraction_theta_max 0.998
_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     15.00 107.72   0.38    0.48    --   67.78-116.00  97.00  244
  2  \w     38.00 137.94   0.38    0.48    --   67.78-165.00 -50.00  263
  3  \w     -7.00  97.88   0.38    0.48    --   67.78 -77.00  30.00  276
  4  \w     37.00 141.88   0.38    0.48    --   67.78  77.00 -30.00  276
  5  \w     52.00 141.68   0.38    0.48    --   67.78 165.00 -26.00  236
  6  \w     85.00 139.72   0.38    0.48    --   67.78 116.00-174.00  144
  7  \w    -25.00  72.66   0.38    0.18    --   -0.47  57.00-150.00  257
  8  \w    -25.00  72.66   0.38    0.18    --   -0.47  57.00-150.00  257
  9  \w    -97.00 -45.70   0.38    0.48    --  -68.72  77.00   0.00  135
 10  \w    -93.00   4.66   0.38    0.48    --  -68.72  57.00 -30.00  257
 11  \w    -89.00  -0.84   0.38    0.48    --  -68.72  77.00   0.00  232
 12  \w    -25.00  72.66   0.38    0.18    --   -0.47  57.00 120.00  257
 13  \w    -68.00 -34.94   0.38    0.48    --  -68.72  38.00-120.00   87
 14  \w   -121.00 -94.78   0.38    0.48    --  -68.72 -57.00 -30.00   69
 15  \w   -143.00 -45.34   0.38    0.48    --  -68.72 -57.00 -30.00  257
 16  \w   -138.00 -39.20   0.38    0.48    --  -68.72 165.00 -26.00  260
 17  \w   -109.00 -16.28   0.38    0.48    --  -68.72 116.00-174.00  244
 18  \w   -143.00 -45.34   0.38    0.48    --  -68.72 -57.00  90.00  257
 19  \w   -143.00 -46.86   0.38    0.48    --  -68.72 -57.00 120.00  253
 20  \w   -144.00 -53.18   0.38    0.48    --  -68.72-165.00 -50.00  239
 21  \w   -144.00 -53.18   0.38    0.48    --  -68.72-165.00 -50.00  239
 22  \w   -142.00 -80.06   0.38    0.48    --  -68.72-125.00  60.00  163
 23  \w   -142.00 -85.00   0.38    0.48    --  -68.72-116.00  97.00  150
 24  \w   -142.00 -80.06   0.38    0.48    --  -68.72-125.00 150.00  163
 25  \w   -144.00 -89.28   0.38    0.48    --  -68.72 -99.00  30.00  144
 26  \w     -8.00  38.74   0.38    0.18    --   -0.47 -99.00 -60.00  123
 27  \w     -8.00  38.74   0.38    0.18    --   -0.47 -99.00   0.00  123
;
_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      0.0329945000
_diffrn_orient_matrix_UB_12      0.0341933000
_diffrn_orient_matrix_UB_13      -0.0451335000
_diffrn_orient_matrix_UB_21      0.0785354000
_diffrn_orient_matrix_UB_22      0.0648254000
_diffrn_orient_matrix_UB_23      0.0354985000
_diffrn_orient_matrix_UB_31      0.0672602000
_diffrn_orient_matrix_UB_32      -0.0463306000
_diffrn_orient_matrix_UB_33      -0.0088906000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'micro-focus metaljet'
_diffrn_radiation_wavelength     1.3405
_diffrn_reflns_av_R_equivalents  0.0359
_diffrn_reflns_av_unetI/netI     0.0284
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       28
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            83098
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        52.931
_diffrn_reflns_theta_max         52.931
_diffrn_reflns_theta_min         2.487
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    0.617
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.56664
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.116a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_colour_primary    black
_exptl_crystal_density_diffrn    1.138
_exptl_crystal_description       block
_exptl_crystal_F_000             1724
_exptl_crystal_size_max          0.71
_exptl_crystal_size_mid          0.71
_exptl_crystal_size_min          0.13
_refine_diff_density_max         1.408
_refine_diff_density_min         -0.474
_refine_diff_density_rms         0.085
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.044
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1121
_refine_ls_number_reflns         16871
_refine_ls_number_restraints     852
_refine_ls_restrained_S_all      1.029
_refine_ls_R_factor_all          0.0858
_refine_ls_R_factor_gt           0.0752
_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^)+(0.0435P)^2^+22.5223P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1746
_refine_ls_wR_factor_ref         0.1797
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14463
_reflns_number_total             16871
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5mh01254f4.cif
_cod_data_source_block           9652_auto
_cod_database_code               1575582
_shelx_shelxl_version_number     2018/3
_cell_oxdiff_angle_alpha         102.0309(11)
_cell_oxdiff_angle_beta          92.1562(11)
_cell_oxdiff_angle_gamma         108.3257(12)
_cell_oxdiff_length_a            13.07877(17)
_cell_oxdiff_length_b            16.7275(2)
_cell_oxdiff_length_c            23.7123(3)
_cell_oxdiff_measurement_reflns_used 42025
_cell_oxdiff_volume              4786.58(10)
_shelx_estimated_absorpt_t_max   0.924
_shelx_estimated_absorpt_t_min   0.669
_diffrn_oxdiff_digest_hkl
;
011acaf7a37d8e4d646b8779389fd8eccbaa5f
;
_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. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
3.a Aromatic/amide H refined with riding coordinates:
 C4(H4), C13(H13), C20(H20), C26(H26), C29(H29), C30(H30), C32(H32), C34(H34),
 C38(H38), C39(H39), C44(H44), C45(H45), C46(H46), C50(H50), C52(H52), C56(H56),
  C62(H62), C64(H64), C70(H70), C78(H78), C79(H79), C80(H80), C82(H82),
 C86(H86), C87(H87), C89(H89), C90(H90), C93(H93), C97(H97), C99(H99),
 C100(H100), C104(H104), C107(H107), C108(H108), C109(H109), C111(H111),
 C112(H112), C9(H9), C18(H18), C31(H31), C36(H36), C37(H37), C40(H40), C41(H41),
  C47(H47), C48(H48), C49(H49), C53(H53), C55(H55), C57(H57), C59(H59),
 C60(H60), C68(H68), C71(H71), C76(H76), C77(H77), C83(H83), C84(H84), C85(H85),
  C88(H88), C91(H91), C92(H92), C94(H94), C95(H95), C96(H96), C98(H98),
 C101(H101), C102(H102), C103(H103), C105(H105), C106(H106), C110(H110),
 C113(H113), C115(H115)
3.b Idealised Me refined as rotating group:
 C67(H67A,H67B,H67C), C69(H69A,H69B,H69C), C63(H63A,H63B,H63C), C73(H73A,H73B,
 H73C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              23302
_shelx_fab_checksum              63592
_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 1.560
_oxdiff_exptl_absorpt_empirical_full_min 0.622