Phototoxicity of hydroxymethyl-BODIPYs: are photocages that innocent?
Kuznetsov, Kirill M.; Mesdom, Pierre; Purkait, Kallol; Blacque, Olivier; Winter, Arthur H.; Cariou, Kevin; Gasser, Gilles; Chemical science 16 (2025) 14553–14563; doi:10.1039/d5sc04032a

data_1575078
_publ_section_title
;
 Phototoxicity of hydroxymethyl-BODIPYs: are photocages that innocent?
;
_journal_issue                   32
_journal_name_full               'Chemical science'
_journal_page_first              14553
_journal_page_last               14563
_journal_paper_doi               10.1039/d5sc04032a
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C30 H25 B Br2 F2 N2 O3'
_chemical_formula_sum            'C30 H25 B Br2 F2 N2 O3'
_chemical_formula_weight         670.15
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-12-18
_audit_creation_method
;
Olex2 1.5-ac6-012
(compiled 2023.08.24 svn.re1ec1418 for Rigaku Oxford Diffraction, GUI svn.r6817)
;
_audit_update_record
;
2025-05-27 deposited with the CCDC.	2025-07-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.3839(19)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   7.88303(17)
_cell_length_b                   9.5602(3)
_cell_length_c                   36.0425(8)
_cell_measurement_reflns_used    6287
_cell_measurement_temperature    160.0(1)
_cell_measurement_theta_max      78.9160
_cell_measurement_theta_min      4.7740
_cell_volume                     2711.55(12)
_computing_cell_refinement       'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.128a 64-bit (release 20-06-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.136a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5-ac6-012 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-012 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015b)'
_computing_structure_solution    'SHELXT (Sheldrick, 2015a)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      160.0(1)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_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    -77.00  22.00   0.50    2.75    --  -50.00  92.00 134.00  198
  2  \w    -19.00  78.00   0.50    2.75    --   50.00 -92.00  21.00  194
  3  \w    -79.00 -18.00   0.50   10.99    --  -90.00  92.00 134.00  122
  4  \w     41.00 105.00   0.50   10.99    --  111.50 -92.00  21.00  128
  5  \w    102.00 178.00   0.50   10.99    --  111.50  92.00 134.00  152
  6  \w    102.00 178.00   0.50   10.99    --  111.50  92.00 134.00  152
  7  \w    -58.00  22.00   0.50    2.75    --  -50.00  38.00 -90.00  160
  8  \w    -85.00 -29.00   0.50    2.75    --  -50.00 125.00 -90.00  112
  9  \w     34.00  94.00   0.50    2.75    --   50.00-125.00  30.00  120
 10  \w      0.00  71.00   0.50    2.75    --   50.00 -77.00 -60.00  142
 11  \w   -161.00-127.00   0.50   10.99    --  -90.00 -61.00-120.00   68
 12  \w   -161.00 -80.00   0.50   10.99    --  -90.00 -92.00  21.00  162
 13  \w   -161.00-127.00   0.50   10.99    --  -90.00 -61.00 150.00   68
 14  \w   -161.00-126.00   0.50   10.99    --  -90.00 -77.00 120.00   70
 15  \w    122.00 149.00   0.50   10.99    --  111.50  45.00-180.00   54
 16  \w     53.00 119.00   0.50   10.99    --  111.50 -30.00   0.00  132
 17  \w     53.00 104.00   0.50   10.99    --  111.50 -45.00   0.00  102
 18  \w    127.00 152.00   0.50   10.99    --  111.50  61.00-150.00   50
 19  \w     43.00 115.00   0.50   10.99    --  111.50 -45.00  90.00  144
 20  \w    127.00 178.00   0.50   10.99    --  111.50  77.00  90.00  102
 21  \w     46.00  94.00   0.50   10.99    --  111.50 -95.00   0.00   96
 22  \w    133.00 158.00   0.50   10.99    --  111.50  61.00  60.00   50
 23  \w    129.00 178.00   0.50   10.99    --  111.50  61.00-180.00   98
 24  \w     42.00  86.00   0.50   10.99    --  111.50 -95.00 120.00   88
 25  \w    147.00 178.00   0.50   10.99    --  111.50  77.00   0.00   62
 26  \w    128.00 154.00   0.50   10.99    --  111.50  77.00-150.00   52
 27  \w     78.00 104.00   0.50   10.99    --  111.50-125.00-180.00   52
 28  \w    128.00 155.00   0.50   10.99    --  111.50  45.00  90.00   54
 29  \w    -52.00 -27.00   0.50    2.75    --  -50.00  92.00 134.00   50
 30  \w    -52.00 -27.00   0.50    2.75    --  -50.00  92.00 134.00   50
 31  \w   -123.00 -98.00   0.50    2.75    --  -50.00 -19.00-120.00   50
 32  \w   -123.00 -42.00   0.50    2.75    --  -50.00 -19.00  90.00  162
 33  \w     49.00  74.00   0.50   10.99    --  111.50 -92.00  21.00   50
 34  \w    147.00 178.00   0.50   10.99    --  111.50  15.00 -60.00   62
 35  \w     67.00  93.00   0.50   10.99    --  111.50-125.00 150.00   52
 36  \w     52.00  78.00   0.50   10.99    --  111.50-125.00  30.00   52
 37  \w     85.00 111.00   0.50   10.99    --  111.50-125.00  30.00   52
 38  \w    135.00 172.00   0.50   10.99    --  111.50  77.00  60.00   74
 39  \w    145.00 174.00   0.50   10.99    --  111.50  61.00 -90.00   58
 40  \w     66.00  95.00   0.50   10.99    --  111.50 -77.00 -60.00   58
 41  \w     50.00  96.00   0.50   10.99    --  111.50 -45.00  60.00   92
 42  \w     47.00  73.00   0.50   10.99    --  111.50 -95.00  90.00   52
 43  \w     56.00  94.00   0.50   10.99    --  111.50-125.00 -60.00   76
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0430456000
_diffrn_orient_matrix_UB_12      -0.0316687000
_diffrn_orient_matrix_UB_13      -0.0413805000
_diffrn_orient_matrix_UB_21      -0.0677527000
_diffrn_orient_matrix_UB_22      -0.1450607000
_diffrn_orient_matrix_UB_23      0.0104620000
_diffrn_orient_matrix_UB_31      -0.1784733000
_diffrn_orient_matrix_UB_32      0.0624537000
_diffrn_orient_matrix_UB_33      0.0032745000
_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  0.0548
_diffrn_reflns_av_unetI/netI     0.0312
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            36993
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         77.380
_diffrn_reflns_theta_min         2.456
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.220
_exptl_absorpt_correction_T_max  0.933
_exptl_absorpt_correction_T_min  0.559
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.136a (Rigaku Oxford Diffraction, 2024)
Analytical numeric absorption correction using a multifaceted crystal
model based on expressions derived by R.C. Clark & J.S. Reid.
(Clark, R. C. & Reid, J. S. (1995). Acta Cryst. A51, 887-897)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            green
_exptl_crystal_density_diffrn    1.642
_exptl_crystal_description       plate
_exptl_crystal_F_000             1344
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.10
_exptl_crystal_size_min          0.02
_refine_diff_density_max         0.758
_refine_diff_density_min         -1.085
_refine_diff_density_rms         0.108
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.194
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     365
_refine_ls_number_reflns         5738
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.194
_refine_ls_R_factor_all          0.0669
_refine_ls_R_factor_gt           0.0572
_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^)+(0.0173P)^2^+15.3786P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1396
_refine_ls_wR_factor_ref         0.1441
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4857
_reflns_number_total             5738
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc04032a2.cif
_cod_data_source_block           11
_cod_depositor_comments          'Adding full bibliography for 1575078.cif.'
_cod_original_cell_volume        2711.55(11)
_cod_database_code               1575078
_shelx_estimated_absorpt_t_max   0.920
_shelx_estimated_absorpt_t_min   0.355
_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:
 C11(H11), C13(H13), C14(H14), C16(H16), C17(H17), C19(H19), C20(H20),
 C22(H22), C23(H23), C25(H25), C26(H26), C28(H28), C29(H29)
2.b Idealised Me refined as rotating group:
 C10(H10A,H10B,H10C), C12(H12A,H12B,H12C), C21(H21A,H21B,H21C), C30(H30A,H30B,
 H30C)
;
_shelx_res_checksum              27783