Effects of phosphorus(V)-substituted 1,3,4-thiadiazoles on the electronic properties of BODIPY fluorophores
Uvarov, Denis Y.; Lesnikov, Vladislav K.; Golovanov, Ivan S.; Burikov, Sergey A.; Salnikova, Diana I.; Scherbakov, Alexander M.; Zavarzin, Igor V.; Volkova, Yulia A.; New Journal of Chemistry 49 (2025) 15885–15894; doi:10.1039/D5NJ01910A

data_7063949
_publ_section_title
;
 Effects of phosphorus(V)-substituted 1,3,4-thiadiazoles on the electronic
 properties of BODIPY fluorophores
;
_journal_issue                   36
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              15885
_journal_page_last               15894
_journal_paper_doi               10.1039/D5NJ01910A
_journal_volume                  49
_journal_year                    2025
_chemical_formula_moiety         'C39 H57 B F2 N10 O2 P2 S2, C8 H2 Cl2 N2 O2'
_chemical_formula_sum            'C47 H59 B Cl2 F2 N12 O4 P2 S2'
_chemical_formula_weight         1101.83
_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   mixed
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2024-07-09
_audit_creation_method
;
Olex2 1.3
(compiled 2019.09.11 svn.r3662 for OlexSys, GUI svn.r5938)
;
_audit_update_record
;
2025-04-25 deposited with the CCDC.	2025-07-21 downloaded from the CCDC.
;
_cell_angle_alpha                69.0631(7)
_cell_angle_beta                 78.1859(7)
_cell_angle_gamma                71.2137(7)
_cell_formula_units_Z            2
_cell_length_a                   15.30926(13)
_cell_length_b                   15.86213(10)
_cell_length_c                   16.43388(13)
_cell_measurement_reflns_used    79562
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      80.5370
_cell_measurement_theta_min      2.8710
_cell_volume                     3510.52(5)
_computing_cell_refinement       'CrysAlisPro 1.171.43.124a (Rigaku OD, 2024)'
_computing_data_collection
'CrysAlisPro system (CCD 43.124a 64-bit (release 23-05-2024))'
_computing_data_reduction        'CrysAlisPro 1.171.43.124a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL n/a (Sheldrick, 2008)'
_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 0.999
_diffrn_measured_fraction_theta_max 0.988
_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    -82.00   0.00   0.50    0.50    --  -44.25 108.00 135.00  164
  2  \w     21.00  85.00   0.50    0.50    --   44.25-108.00  39.00  128
  3  \w    -81.00 -25.00   0.50    2.00    --  -96.00 108.00 135.00  112
  4  \w   -167.00 -82.00   0.50    2.00    --  -96.00-108.00  39.00  170
  5  \w     46.00 107.00   0.50    2.00    --  117.50-108.00  39.00  122
  6  \w    104.00 178.00   0.50    2.00    --  117.50 108.00 135.00  148
  7  \w    -27.00  35.00   0.50    0.50    --  -44.25  19.00  30.00  124
  8  \w    -27.00  35.00   0.50    0.50    --  -44.25  19.00  90.00  124
  9  \w   -117.00 -17.00   0.50    0.50    --  -44.25 -77.00  90.00  200
 10  \w    -27.00  35.00   0.50    0.50    --  -44.25  19.00 -30.00  124
 11  \w    -86.00 -13.00   0.50    0.50    --  -44.25 125.00-150.00  146
 12  \w   -117.00 -17.00   0.50    0.50    --  -44.25 -77.00  90.00  200
 13  \w     34.00  94.00   0.50    0.50    --   44.25-125.00 -90.00  120
 14  \w    -34.00  27.00   0.50    0.50    --   44.25 -19.00 120.00  122
 15  \w     25.00 118.00   0.50    0.50    --   44.25  57.00-180.00  186
 16  \w    -28.00  64.00   0.50    0.50    --   44.25 -57.00   0.00  184
 17  \w     25.00 118.00   0.50    0.50    --   44.25  57.00-180.00  186
 18  \w    -28.00  64.00   0.50    0.50    --   44.25 -57.00   0.00  184
 19  \w   -170.00 -75.00   0.50    2.00    --  -96.00 -61.00 114.43  190
 20  \w     45.00 105.00   0.50    2.00    --  117.50 -77.00 120.00  120
 21  \w     47.00 111.00   0.50    2.00    --  117.50-125.00   0.00  128
 22  \w     45.00 105.00   0.50    2.00    --  117.50 -95.00  90.00  120
 23  \w     47.00 111.00   0.50    2.00    --  117.50-125.00-180.00  128
 24  \w     98.00 178.00   0.50    2.00    --  117.50  30.00 150.00  160
 25  \w     98.00 178.00   0.50    2.00    --  117.50  45.00-150.00  160
 26  \w     45.00  71.00   0.50    2.00    --  117.50 -61.00 -90.00   52
 27  \w     98.00 178.00   0.50    2.00    --  117.50  45.00   0.00  160
 28  \w     45.00 105.00   0.50    2.00    --  117.50 -77.00 150.00  120
 29  \w     95.00 178.00   0.50    2.00    --  117.50 125.00-120.00  166
 30  \w     98.00 178.00   0.50    2.00    --  117.50  45.00-150.00  160
 31  \w     97.00 178.00   0.50    2.00    --  117.50  61.00-120.00  162
 32  \w     86.00 178.00   0.50    2.00    --  117.50  15.00   0.00  184
 33  \w     45.00 105.00   0.50    2.00    --  117.50 -95.00-120.00  120
 34  \w     86.00 178.00   0.50    2.00    --  117.50  15.00  60.00  184
 35  \w     47.00 111.00   0.50    2.00    --  117.50-125.00 -30.00  128
 36  \w     47.00 111.00   0.50    2.00    --  117.50-125.00 -30.00  128
 37  \w     45.00  71.00   0.50    2.00    --  117.50 -61.00  30.00   52
 38  \w     95.00 178.00   0.50    2.00    --  117.50 125.00-150.00  166
 39  \w     95.00 178.00   0.50    2.00    --  117.50 125.00-150.00  166
 40  \w     45.00  71.00   0.50    2.00    --  117.50 -61.00 -60.00   52
 41  \w     97.00 178.00   0.50    2.00    --  117.50  61.00-180.00  162
 42  \w     45.00  71.00   0.50    2.00    --  117.50 -61.00  90.00   52
 43  \w     98.00 178.00   0.50    2.00    --  117.50  30.00-180.00  160
 44  \w     55.00 110.00   0.50    2.00    --  117.50-125.00  60.00  110
 45  \w    128.00 161.00   0.50    2.00    --  117.50 125.00   0.00   66
 46  \w     43.00 113.00   0.50    2.00    --  117.50   0.00-120.00  140
 47  \w    148.00 178.00   0.50    2.00    --  117.50   0.00-120.00   60
 48  \w     47.00 105.00   0.50    2.00    --  117.50 -95.00  60.00  116
 49  \w     45.00  70.00   0.50    2.00    --  117.50 -61.00 120.00   50
 50  \w    118.00 176.00   0.50    2.00    --  117.50  61.00  60.00  116
 51  \w     77.00 105.00   0.50    2.00    --  117.50 -95.00 120.00   56
 52  \w     46.00  99.00   0.50    2.00    --  117.50 -77.00-150.00  106
 53  \w     54.00  82.00   0.50    2.00    --  117.50 -95.00-150.00   56
 54  \w     49.00  75.00   0.50    2.00    --  117.50 -80.00  61.59   52
 55  \w     45.00  94.00   0.50    2.00    --  117.50 -77.00 -60.00   98
 56  \w     62.00  87.00   0.50    2.00    --  117.50 -95.00  30.00   50
 57  \w    113.00 140.00   0.50    2.00    --  117.50 -87.00  37.32   54
 58  \w     86.00 158.00   0.50    2.00    --  117.50  15.00  30.00  144
 59  \w     75.00 111.00   0.50    2.00    --  117.50-125.00-120.00   72
 60  \w     45.00  70.00   0.50    2.00    --  117.50 -61.00 150.00   50
 61  \w     83.00 110.00   0.50    2.00    --  117.50-125.00 -60.00   54
 62  \w    107.00 157.00   0.50    2.00    --  117.50  15.00-180.00  100
 63  \w     83.00 111.00   0.50    2.00    --  117.50-125.00  30.00   56
 64  \w    153.00 178.00   0.50    2.00    --  117.50  61.00 -90.00   50
 65  \w    109.00 148.00   0.50    2.00    --  117.50  45.00  90.00   78
 66  \w     66.00  93.00   0.50    2.00    --  117.50 -77.00 -90.00   54
 67  \w     46.00  72.00   0.50    2.00    --  117.50 -77.00  90.00   52
 68  \w     45.00  75.00   0.50    2.00    --  117.50 -95.00 -90.00   60
 69  \w     47.00  76.00   0.50    2.00    --  117.50-125.00 -60.00   58
 70  \w     98.00 153.00   0.50    2.00    --  117.50  45.00-180.00  110
 71  \w    123.00 148.00   0.50    2.00    --  117.50 -84.00  43.94   50
 72  \w     47.00 111.00   0.50    2.00    --  117.50-125.00-150.00  128
 73  \w    146.00 172.00   0.50    2.00    --  117.50  61.00  30.00   52
 74  \w     51.00  77.00   0.50    2.00    --  117.50 -84.00  43.94   52
 75  \w     98.00 143.00   0.50    2.00    --  117.50  45.00  30.00   90
 76  \w     98.00 131.00   0.50    2.00    --  117.50  45.00 120.00   66
 77  \w    108.00 171.00   0.50    2.00    --  117.50  15.00 -90.00  126
 78  \w     69.00 110.00   0.50    2.00    --  117.50 -78.00-159.50   82
 79  \w     53.00  79.00   0.50    2.00    --  117.50 -83.00  76.74   52
 80  \w     94.00 120.00   0.50    2.00    --  117.50 -83.00  76.74   52
 81  \w     83.00 111.00   0.50    2.00    --  117.50-125.00 120.00   56
 82  \w    108.00 135.00   0.50    2.00    --  117.50  30.00-120.00   54
 83  \w    138.00 163.00   0.50    2.00    --  117.50  30.00-120.00   50
 84  \w     95.00 120.00   0.50    2.00    --  117.50 125.00   0.00   50
 85  \w    153.00 178.00   0.50    2.00    --  117.50  30.00  90.00   50
 86  \w    129.00 178.00   0.50    2.00    --  117.50 125.00  30.00   98
 87  \w    100.00 129.00   0.50    2.00    --  117.50 125.00  60.00   58
 88  \w    139.00 165.00   0.50    2.00    --  117.50 125.00  60.00   52
 89  \w     45.00 104.00   0.50    2.00    --  117.50 -95.00 150.00  118
 90  \w     80.00 105.00   0.50    2.00    --  117.50 -95.00 -90.00   50
 91  \w     48.00  82.00   0.50    2.00    --  117.50 -81.00 -89.38   68
 92  \w    100.00 126.00   0.50    2.00    --  117.50 -81.00 -89.38   52
 93  \w     48.00  73.00   0.50    2.00    --  117.50 -87.00 140.62   50
 94  \w    118.00 147.00   0.50    2.00    --  117.50 -87.00 140.62   58
 95  \w     52.00 103.00   0.50    2.00    --  117.50 -95.00 -60.00  102
 96  \w     46.00  74.00   0.50    2.00    --  117.50 -95.00   0.00   56
 97  \w     98.00 142.00   0.50    2.00    --  117.50  30.00  90.00   88
 98  \w    119.00 145.00   0.50    2.00    --  117.50  45.00-120.00   52
 99  \w    125.00 151.00   0.50    2.00    --  117.50  45.00 -60.00   52
100  \w    139.00 165.00   0.50    2.00    --  117.50  30.00  30.00   52
101  \w    100.00 143.00   0.50    2.00    --  117.50  61.00  30.00   86
102  \w    116.00 142.00   0.50    2.00    --  117.50  61.00 -90.00   52
103  \w    134.00 172.00   0.50    2.00    --  117.50 125.00 120.00   76
104  \w    100.00 138.00   0.50    2.00    --  117.50 -81.00 -67.34   76
105  \w     47.00  74.00   0.50    2.00    --  117.50 -85.00  -3.31   54
106  \w    122.00 147.00   0.50    2.00    --  117.50 -85.00  -3.31   50
107  \w     46.00  72.00   0.50    2.00    --  117.50 -87.00 -17.72   52
108  \w    111.00 148.00   0.50    2.00    --  117.50 -87.00 -17.72   74
109  \w     84.00 110.00   0.50    2.00    --  117.50-125.00 -90.00   52
110  \w     90.00 116.00   0.50    2.00    --  117.50 -88.00  59.12   52
111  \w     45.00  70.00   0.50    2.00    --  117.50 -61.00-180.00   50
;
_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      -0.1048892000
_diffrn_orient_matrix_UB_12      0.0214509000
_diffrn_orient_matrix_UB_13      -0.0039317000
_diffrn_orient_matrix_UB_21      0.0176891000
_diffrn_orient_matrix_UB_22      0.0093462000
_diffrn_orient_matrix_UB_23      -0.0981548000
_diffrn_orient_matrix_UB_31      0.0100351000
_diffrn_orient_matrix_UB_32      -0.1055063000
_diffrn_orient_matrix_UB_33      0.0230033000
_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  0.0306
_diffrn_reflns_av_unetI/netI     0.0181
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            110783
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.818
_diffrn_reflns_theta_min         2.894
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.209
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.287
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.124a (Rigaku Oxford Diffraction, 2024)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            pink
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.042
_exptl_crystal_description       prism
_exptl_crystal_F_000             1152
_exptl_crystal_size_max          0.31
_exptl_crystal_size_mid          0.24
_exptl_crystal_size_min          0.14
_refine_diff_density_max         0.446
_refine_diff_density_min         -0.378
_refine_diff_density_rms         0.051
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     705
_refine_ls_number_reflns         15256
_refine_ls_number_restraints     10
_refine_ls_restrained_S_all      1.031
_refine_ls_R_factor_all          0.0359
_refine_ls_R_factor_gt           0.0350
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0565P)^2^+1.3005P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0978
_refine_ls_wR_factor_ref         0.0985
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14605
_reflns_number_total             15256
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj01910a2.cif
_cod_data_source_block           mrin007f3-pink
_cod_depositor_comments          'Adding full bibliography for 7063949.cif.'
_cod_database_code               7063949
_shelxl_version_number           2014/6
_chemical_oxdiff_formula         C55H77Cl6N12O6
_chemical_oxdiff_usercomment     Mrin007f2-pinkprism
_shelx_estimated_absorpt_t_max   0.747
_shelx_estimated_absorpt_t_min   0.548
_reflns_odcompleteness_completeness 98.10
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     81.42
_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, All C(H,H,H,H,H,H) groups
2. Restrained distances
 C31A-C32A \\sim C31-C32
 with sigma of 0.02
 C32-C27 \\sim C27-C32A
 with sigma of 0.02
 C28A-C27 \\sim C27-C28
 with sigma of 0.02
 C28A-C29A \\sim C28-C29
 with sigma of 0.02
 C29A-C30A \\sim C29-C30
 with sigma of 0.02
 C30A-C31A \\sim C30-C31
 with sigma of 0.02
 C49A-C46A \\sim C49-C46
 with sigma of 0.02
 C48A-C46A \\sim C46-C48
 with sigma of 0.02
 C46-C47 \\sim C47-C46A
 with sigma of 0.02
 C46A-N45 \\sim N45-C46
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C31) = Uanis(C31A)
Uanis(C32A) = Uanis(C32)
Uanis(C28) = Uanis(C28A)
Uanis(C29) = Uanis(C29A)
Uanis(C32A) = Uanis(C32) = Uanis(C28) = Uanis(C28A)
Uanis(C31A) = Uanis(C31) = Uanis(C29) = Uanis(C29A)
Uanis(C30A) = Uanis(C30)
Uanis(C46) = Uanis(C46A)
Uanis(C48) = Uanis(C48A)
Uanis(C49) = Uanis(C49A)
4. Others
 Sof(C28A)=Sof(H28A)=Sof(C29A)=Sof(H29A)=Sof(C30A)=Sof(H30A)=Sof(C31A)=
 Sof(H31A)=Sof(C32A)=Sof(H32A)=1-FVAR(1)
 Sof(C28)=Sof(H28)=Sof(C29)=Sof(H29)=Sof(C30)=Sof(H30)=Sof(C31)=Sof(H31)=
 Sof(C32)=Sof(H32)=FVAR(1)
 Sof(C46A)=Sof(H47D)=Sof(H47E)=Sof(H47F)=Sof(C48A)=Sof(H48D)=Sof(H48E)=
 Sof(H48F)=Sof(C49A)=Sof(H49D)=Sof(H49E)=Sof(H49F)=1-FVAR(2)
 Sof(C46)=Sof(H47A)=Sof(H47B)=Sof(H47C)=Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(H48C)=
 Sof(C49)=Sof(H49A)=Sof(H49B)=Sof(H49C)=FVAR(2)
5.a Aromatic/amide H refined with riding coordinates:
 C28(H28), C28A(H28A), C29(H29), C29A(H29A), C30(H30), C30A(H30A), C31(H31),
 C31A(H31A), C32(H32), C32A(H32A)
5.b Idealised Me refined as rotating group:
 C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,
 H26C), C36(H36A,H36B,H36C), C37(H37A,H37B,H37C), C38(H38A,H38B,H38C), C41(H41A,
 H41B,H41C), C42(H42A,H42B,H42C), C43(H43A,H43B,H43C), C47(H47A,H47B,H47C),
 C47(H47D,H47E,H47F), C48(H48A,H48B,H48C), C48A(H48D,H48E,H48F), C49(H49A,H49B,
 H49C), C49A(H49D,H49E,H49F), C52(H52A,H52B,H52C), C53(H53A,H53B,H53C),
 C54(H54A,H54B,H54C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              78200
_shelx_fab_checksum              32050
_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 1.328
_oxdiff_exptl_absorpt_empirical_full_min 0.772