Synthesis, photophysics and photosensitizing hydrogen evolution of a near-infrared heavy-atom-free sensitizer
Lin, Ming-Sui; Nie, Qing-Bin; Chen, Jia-Nan; Liu, Ze-Yu; Wu, Qiao-Yu; Liu, Xiao-Feng; Liu, Chao; Pan, Zhong-Hua; Xiao, Wang-Chuan; Luo, Geng-Geng; New Journal of Chemistry 49 (2025) 7647–7654; doi:10.1039/D5NJ00537J

data_7063739
_publ_section_title
;
 Synthesis, photophysics and photosensitizing hydrogen evolution of a
 near-infrared heavy-atom-free sensitizer
;
_journal_issue                   18
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              7647
_journal_page_last               7654
_journal_paper_doi               10.1039/D5NJ00537J
_journal_volume                  49
_journal_year                    2025
_chemical_formula_moiety         '2(C28 H14 B F2 N3 S4), 0.858[CH2Cl2]'
_chemical_formula_sum            'C28 H14 B F2 N3 S4'
_chemical_formula_weight         569.47
_chemical_name_systematic        C56H28B2F4N6S8
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     iterative
_audit_creation_date             2025-03-24
_audit_creation_method
;
Olex2 1.5
(compiled 2025.03.04 svn.red2d20d0 for OlexSys, GUI svn.r7188)
;
_audit_update_record
;
2025-03-25 deposited with the CCDC.	2025-04-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 104.5070(10)
_cell_angle_gamma                90
_cell_formula_units_Z            16
_cell_length_a                   19.6846(2)
_cell_length_b                   18.41220(10)
_cell_length_c                   29.7761(2)
_cell_measurement_reflns_used    24790
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      76.6300
_cell_measurement_theta_min      2.8350
_cell_volume                     10447.87(15)
_computing_cell_refinement       'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.80a (Rigaku OD, 2020)'
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_temperature      100.00
_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     33.00  60.00   0.50    0.20    --  104.80 -61.00-180.00   54
  2  \w     36.00  69.00   0.50    0.20    --  104.80 -61.00 -90.00   66
  3  \w     44.00  69.00   0.50    0.20    --  104.80 -61.00 -30.00   50
  4  \w     40.00  83.00   0.50    0.20    --  104.80 -67.00  32.00   86
  5  \w    -22.00  48.00   0.50    0.05    --   47.89 -67.00  32.00  140
  6  \w     94.00 124.00   0.50    0.20    --  104.80  45.00  90.00   60
  7  \w    147.00 176.00   0.50    0.20    --  104.80  67.00 166.00   58
  8  \w     51.00  76.00   0.50    0.05    --   47.89  67.00 166.00   50
  9  \w     63.00  96.00   0.50    0.20    --  104.80 -94.00  90.00   66
 10  \w     34.00  99.00   0.50    0.20    --  104.80 -94.00-150.00  130
 11  \w    -24.00  23.00   0.50    0.05    --  -47.89  19.00-180.00   94
 12  \w    -20.00  24.00   0.50    0.05    --  -47.89  19.00 -30.00   88
 13  \w     -5.00  24.00   0.50    0.05    --  -47.89  67.00 166.00   58
 14  \w    -69.00 -44.00   0.50    0.20    --  -99.00  61.00   0.00   50
 15  \w   -102.00 -69.00   0.50    0.20    --  -99.00  77.00   0.00   66
 16  \w    -66.00 -33.00   0.50    0.20    --  -99.00  77.00   0.00   66
 17  \w    -61.00 -30.00   0.50    0.20    --  -99.00  67.00 166.00   62
 18  \w    -69.00 -40.00   0.50    0.20    --  -99.00  61.00 150.00   58
 19  \w   -140.00 -90.00   0.50    0.20    --  -99.00 -15.00  90.00  100
 20  \w   -167.00-141.00   0.50    0.20    --  -99.00 -15.00  90.00   52
 21  \w   -166.00 -86.00   0.50    0.20    --  -99.00 -67.00  32.00  160
 22  \w   -110.00 -45.00   0.50    0.05    --  -47.89 -67.00  32.00  130
 23  \w   -167.00 -90.00   0.50    0.20    --  -99.00 -45.00 -90.00  154
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0329
_diffrn_reflns_av_unetI/netI     0.0292
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            33053
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        66.594
_diffrn_reflns_theta_max         66.594
_diffrn_reflns_theta_min         2.848
_exptl_absorpt_coefficient_mu    3.670
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.87819
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.80a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'metallic brownish brown'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   brownish
_exptl_crystal_colour_primary    brown
_exptl_crystal_density_diffrn    1.448
_exptl_crystal_description       block
_exptl_crystal_F_000             4640
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.998
_refine_diff_density_min         -1.046
_refine_diff_density_rms         0.062
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     815
_refine_ls_number_reflns         9200
_refine_ls_number_restraints     418
_refine_ls_restrained_S_all      1.037
_refine_ls_R_factor_all          0.0447
_refine_ls_R_factor_gt           0.0419
_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^)+(0.0375P)^2^+32.7489P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1000
_refine_ls_wR_factor_ref         0.1018
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8497
_reflns_number_total             9200
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nj00537j2.cif
_cod_data_source_block           1
_cod_depositor_comments
'Adding full bibliography for 7063738--7063739.cif.'
_cod_database_code               7063739
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         SBFCN
_shelx_estimated_absorpt_t_max   0.527
_shelx_estimated_absorpt_t_min   0.527
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 S008-C023 = S008-C01W
 1.73 with sigma of 0.001
 S0-C01W = S0-C0
 1.73 with sigma of 0.001
 S1-C01O
 1.73 with sigma of 0.001
 C022-C01W = C026-C023 = C4-C01M = C021-C01X = C01O-C00F = C01Z-C01Y = C020-
 C01S = C01K-C013
 1.39 with sigma of 0.001
 C022-C023 \\sim C2-C0
 with sigma of 0.04
 S008-C01W \\sim S0-C01W
 with sigma of 0.02
 C022-C026 \\sim C2-C1
 with sigma of 0.02
 S008-C023 \\sim S0-C0
 with sigma of 0.02
 C01W-C022 \\sim C01W-C2
 with sigma of 0.02
 S008-C026 \\sim S0-C1
 with sigma of 0.04
 C023-C026 \\sim C0-C1
 with sigma of 0.02
 C01W-C023 \\sim C01W-C0
 with sigma of 0.04
 C01W-C026 \\sim C01W-C1
 with sigma of 0.04
 C01O-C01Y \\sim C01O-C3
 with sigma of 0.04
 C00F-C01O \\sim C00G-C01O
 with sigma of 0.02
 C00F-C01Y \\sim C00G-C3
 with sigma of 0.02
 C01O-C01Z \\sim C01O-C01{
 with sigma of 0.04
 C00F-C01Z \\sim C00G-C01{
 with sigma of 0.04
 C01Y-C01Z \\sim C3-C01{
 with sigma of 0.02
 S007-C01O \\sim S1-C01O
 with sigma of 0.02
 S007-C01Z \\sim S1-C01{
 with sigma of 0.02
 S007-C01Y \\sim S1-C3
 with sigma of 0.04
 S006-C01M \\sim S2-C01M
 with sigma of 0.02
 S006-C021 \\sim S2-C6
 with sigma of 0.02
 C01M-C4 \\sim C01M-C4A
 with sigma of 0.02
 C01X-C021 \\sim C5-C6
 with sigma of 0.02
 C01X-C4 \\sim C5-C4A
 with sigma of 0.02
 S006-C01X \\sim S2-C5
 with sigma of 0.04
 C01M-C01X \\sim C01M-C5
 with sigma of 0.04
 C01M-C021 \\sim C01M-C6
 with sigma of 0.04
 C021-C4 \\sim C6-C4A
 with sigma of 0.04
 S005-C01K \\sim S3-C01K
 with sigma of 0.02
 S005-C020 \\sim S3-C9
 with sigma of 0.02
 C013-C01K \\sim C7-C01K
 with sigma of 0.02
 C013-C01S \\sim C7-C8
 with sigma of 0.02
 C01S-C020 \\sim C8-C9
 with sigma of 0.02
 S005-C01S \\sim S3-C8
 with sigma of 0.04
 C013-C020 \\sim C7-C9
 with sigma of 0.04
 C01K-C01S \\sim C01K-C8
 with sigma of 0.04
 C01K-C020 \\sim C01K-C9
 with sigma of 0.04
3. Rigid bond restraints
 C00F, C01Y
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 S007, C010
 with sigma for 1-2 distances of 0.02 and sigma for 1-3 distances of 0.02
 S007, C01O
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C01V, C022
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C2, C01W, C01Z, C0, C1, S0
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C022 \\sim C2 \\sim C1 \\sim C023 \\sim C026 \\sim C0: within 2A with sigma of
0.001 and sigma for terminal atoms of 0.002 within 2A
S006 \\sim C01M \\sim C01X \\sim C021 \\sim C4 \\sim S2 \\sim C5 \\sim C6 \\sim
C4A: within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002 within
2A
S005 \\sim C013 \\sim C01K \\sim C01S \\sim C020 \\sim S3 \\sim C7 \\sim C8
\\sim C9: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
Uanis(C00F) \\sim Ueq: with sigma of 0.0003 and sigma for terminal atoms of
0.0006
Uanis(C022) \\sim Ueq: with sigma of 0.0003 and sigma for terminal atoms of
0.0006
Uanis(C0) \\sim Ueq, Uanis(C2) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.01
Uanis(S0) \\sim Ueq, Uanis(C0) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C01{)
\\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C00G) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.01
Uanis(C01{) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.001
Uanis(C3) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.001
Uanis(C022) = Uanis(C2)
Uanis(C01{) = Uanis(C01Z)
Uanis(C01Y) = Uanis(C3)
5. Rigid body (RIGU) restrains
 C4, C01X
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
6. Others
 Sof(S0)=Sof(C0)=Sof(H0)=Sof(C1)=Sof(H1)=Sof(C2)=Sof(H2)=1-FVAR(1)
 Sof(S008)=Sof(C022)=Sof(H022)=Sof(C023)=Sof(H023)=Sof(C026)=Sof(H026)=FVAR(1)
 Sof(S1)=Sof(C01{)=Sof(H01{)=Sof(C3)=Sof(H3)=Sof(C00G)=Sof(H00G)=1-FVAR(2)
 Sof(S007)=Sof(C00F)=Sof(H00F)=Sof(C01Y)=Sof(H01Y)=Sof(C01Z)=Sof(H01Z)=FVAR(2)
 Sof(S2)=Sof(C5)=Sof(H5)=Sof(C6)=Sof(H6)=Sof(C4A)=Sof(H4A)=1-FVAR(3)
 Sof(S006)=Sof(C01X)=Sof(H01X)=Sof(C021)=Sof(H021)=Sof(C4)=Sof(H4)=FVAR(3)
 Sof(S3)=Sof(C7)=Sof(H7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(H9)=1-FVAR(4)
 Sof(S005)=Sof(C013)=Sof(H013)=Sof(C01S)=Sof(H01S)=Sof(C020)=Sof(H020)=FVAR(4)
7.a Aromatic/amide H refined with riding coordinates:
 C00F(H00F), C00Q(H00Q), C00V(H00V), C00X(H00X), C00Z(H00Z), C013(H013),
 C014(H014), C015(H015), C016(H016), C017(H017), C01C(H01C), C01E(H01E),
 C01G(H01G), C01H(H01H), C01P(H01P), C01R(H01R), C01S(H01S), C01T(H01T),
 C01V(H01V), C01X(H01X), C01Y(H01Y), C01Z(H01Z), C020(H020), C021(H021),
 C022(H022), C023(H023), C026(H026), C0(H0), C1(H1), C2(H2), C01{(H01{), C3(H3),
  C00G(H00G), C4(H4), C5(H5), C6(H6), C4A(H4A), C7(H7), C8(H8), C9(H9)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 288 electrons were 
found in a volume of 792\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
0.858[CH2Cl2] per Unit Cell 
which account for 288 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              27379
_shelx_hkl_checksum              84686
_shelx_fab_checksum              24893
_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 1.186
_oxdiff_exptl_absorpt_empirical_full_min 0.892