The Role of Exciplex Charge-Transfer Character and Reorganization Energy in Steering Oxygen Quenching Pathways of Chromium(III) Excited States
Amer, Aya S.; Abdel-Shafi, Ayman; Alazaly, Ahmed M. M.; El-Jemni, Mahmoud A.; Hassan, Hamdy Hassanien; Abdel-Samad, Hesham Samir; Dalton Transactions  (2026) –; doi:10.1039/D6DT00398B

data_7720740
_publ_section_title
;
 The role of exciplex charge-transfer character and reorganization energy
 in steering oxygen-quenching pathways of chromium(III) excited states.
;
_journal_issue                   16
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              6373
_journal_page_last               6389
_journal_paper_doi               10.1039/d6dt00398b
_journal_volume                  55
_journal_year                    2026
_chemical_formula_moiety         'C38 H40 Cr N6, 3(C F3 O3 S)'
_chemical_formula_sum            'C41 H40 Cr F9 N6 O9 S3'
_chemical_formula_weight         1079.97
_chemical_name_systematic        'chrmium (III) bipyridines'
_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             2021-04-08
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2025-12-22 deposited with the CCDC.	2026-03-24 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 105.8810(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   19.81110(10)
_cell_length_b                   19.25680(10)
_cell_length_c                   12.00480(10)
_cell_measurement_reflns_used    55576
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      79.6330
_cell_measurement_theta_min      3.2760
_cell_volume                     4405.01(5)
_computing_cell_refinement       'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.99a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (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(2)
_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 0.990
_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    -81.00   2.00   0.50    0.20    --  -47.90 106.00 171.00  166
  2  \w     19.00  85.00   0.50    0.20    --   47.90-106.00  72.00  132
  3  \w    -82.00 -19.00   0.50    0.80    --  -91.75 106.00 171.00  126
  4  \w     42.00 108.00   0.50    0.80    --  113.25-106.00  72.00  132
  5  \w    105.00 178.00   0.50    0.80    --  113.25 106.00 171.00  146
  6  \w   -121.00 -35.00   0.50    0.20    --  -47.90 -37.00-150.00  172
  7  \w   -119.00 -73.00   0.50    0.20    --  -47.90-125.00-120.00   92
  8  \w   -119.00 -73.00   0.50    0.20    --  -47.90-125.00-150.00   92
  9  \w    -63.00  25.00   0.50    0.20    --  -47.90  57.00 150.00  176
 10  \w    -23.00  28.00   0.50    0.20    --  -47.90  19.00  60.00  102
 11  \w   -119.00 -73.00   0.50    0.20    --  -47.90-125.00-180.00   92
 12  \w    -41.00  25.00   0.50    0.20    --  -47.90  37.00 -90.00  132
 13  \w    -23.00  28.00   0.50    0.20    --  -47.90  19.00-150.00  102
 14  \w    -26.00  23.00   0.50    0.20    --   47.90 -19.00   0.00   98
 15  \w     34.00  96.00   0.50    0.20    --   47.90-125.00 150.00  124
 16  \w    -26.00  23.00   0.50    0.20    --   47.90 -19.00  60.00   98
 17  \w    -50.00 -20.00   0.50    0.80    --  -91.75  45.00 120.00   60
 18  \w   -163.00 -77.00   0.50    0.80    --  -91.75 -56.00 -15.00  172
 19  \w   -163.00 -83.00   0.50    0.80    --  -91.75-106.00  72.00  160
 20  \w    -50.00 -20.00   0.50    0.80    --  -91.75  45.00   0.00   60
 21  \w   -163.00 -69.00   0.50    0.80    --  -91.75 -77.00 125.82  188
 22  \w     42.00 111.00   0.50    0.80    --  113.25-125.00 -30.00  138
 23  \w     91.00 178.00   0.50    0.80    --  113.25  77.00 -30.00  174
 24  \w     91.00 178.00   0.50    0.80    --  113.25  77.00 150.00  174
 25  \w    101.00 178.00   0.50    0.80    --  113.25  45.00-150.00  154
 26  \w     43.00  69.00   0.50    0.80    --  113.25-125.00-180.00   52
 27  \w     43.00  68.00   0.50    0.80    --  113.25 -61.00-120.00   50
 28  \w     96.00 140.00   0.50    0.80    --  113.25 125.00-120.00   88
 29  \w     76.00 105.00   0.50    0.80    --  113.25-125.00-180.00   58
 30  \w     79.00 104.00   0.50    0.80    --  113.25 -94.00 -60.00   50
 31  \w     42.00 111.00   0.50    0.80    --  113.25-125.00   0.00  138
 32  \w     42.00  72.00   0.50    0.80    --  113.25 -61.00 150.00   60
 33  \w     63.00  89.00   0.50    0.80    --  113.25 -94.00  30.00   52
 34  \w     42.00  72.00   0.50    0.80    --  113.25 -61.00  30.00   60
 35  \w     44.00 106.00   0.50    0.80    --  113.25 -94.00-120.00  124
 36  \w    138.00 167.00   0.50    0.80    --  113.25  30.00 -30.00   58
 37  \w    144.00 178.00   0.50    0.80    --  113.25  45.00  60.00   68
 38  \w    102.00 134.00   0.50    0.80    --  113.25  45.00  90.00   64
 39  \w    101.00 140.00   0.50    0.80    --  113.25  45.00  60.00   78
 40  \w     42.00 106.00   0.50    0.80    --  113.25 -94.00-180.00  128
 41  \w     92.00 177.00   0.50    0.80    --  113.25  77.00-120.00  170
 42  \w     98.00 129.00   0.50    0.80    --  113.25-149.00-115.91   62
 43  \w     59.00 103.00   0.50    0.80    --  113.25 -94.00-150.00   88
 44  \w     49.00  75.00   0.50    0.80    --  113.25-149.00-115.91   52
 45  \w    152.00 177.00   0.50    0.80    --  113.25  45.00  90.00   50
 46  \w     97.00 176.00   0.50    0.80    --  113.25  61.00  30.00  158
 47  \w    138.00 174.00   0.50    0.80    --  113.25  30.00 150.00   72
 48  \w     78.00 103.00   0.50    0.80    --  113.25 -94.00 -30.00   50
 49  \w     42.00  76.00   0.50    0.80    --  113.25 -94.00 120.00   68
 50  \w     81.00 106.00   0.50    0.80    --  113.25 -94.00 120.00   50
 51  \w     42.00  71.00   0.50    0.80    --  113.25 -61.00-180.00   58
 52  \w     97.00 178.00   0.50    0.80    --  113.25  61.00 -90.00  162
 53  \w     48.00 105.00   0.50    0.80    --  113.25 -94.00   0.00  114
 54  \w     72.00 105.00   0.50    0.80    --  113.25 -94.00  90.00   66
 55  \w     42.00  68.00   0.50    0.80    --  113.25 -94.00  90.00   52
 56  \w    102.00 178.00   0.50    0.80    --  113.25  61.00-150.00  152
 57  \w     74.00  99.00   0.50    0.80    --  113.25 -94.00  60.00   50
 58  \w    148.00 173.00   0.50    0.80    --  113.25  45.00 -60.00   50
 59  \w     46.00  72.00   0.50    0.80    --  113.25 -61.00 120.00   52
 60  \w     43.00  71.00   0.50    0.80    --  113.25 -61.00 -90.00   56
;
_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      -0.0065597000
_diffrn_orient_matrix_UB_12      0.0403783000
_diffrn_orient_matrix_UB_13      0.0659389000
_diffrn_orient_matrix_UB_21      0.0343813000
_diffrn_orient_matrix_UB_22      -0.0661985000
_diffrn_orient_matrix_UB_23      0.0445306000
_diffrn_orient_matrix_UB_31      0.1287007000
_diffrn_orient_matrix_UB_32      0.0197584000
_diffrn_orient_matrix_UB_33      0.0144031000
_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  0.0489
_diffrn_reflns_av_unetI/netI     0.0240
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.990
_diffrn_reflns_limit_h_max       25
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            90358
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.990
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         80.046
_diffrn_reflns_theta_min         3.263
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.375
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88598
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.99a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.628
_exptl_crystal_description       block
_exptl_crystal_F_000             2212
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.08
_refine_diff_density_max         0.412
_refine_diff_density_min         -0.547
_refine_diff_density_rms         0.061
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.079
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     628
_refine_ls_number_reflns         9527
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.079
_refine_ls_R_factor_all          0.0354
_refine_ls_R_factor_gt           0.0337
_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^)+(0.0457P)^2^+2.7971P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0888
_refine_ls_wR_factor_ref         0.0900
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8991
_reflns_number_total             9527
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6dt00398b2.cif
_cod_data_source_block           ae5
_cod_depositor_comments
'Adding full bibliography for 7720740--7720741.cif.'
_cod_database_code               7720740
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H20 N2 O2 S Cr'
_chemical_oxdiff_usercomment     'C20 H20 N2 O2 S Cr yelloe block 0.08 0.1 0.14'
_shelx_estimated_absorpt_t_max   0.721
_shelx_estimated_absorpt_t_min   0.579
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.08
_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:
 C29(H29), C24(H24), C9(H9), C17(H17), C21(H21), C12(H12), C16(H16), C11(H11),
 C3(H3), C10(H10), C15(H15), C14(H14), C4(H4), C5(H5), C36(H36), C22(H22),
 C26(H26), C27(H27), C34(H34), C2(H2), C23(H23), C33(H33)
2.b Idealised Me refined as rotating group:
 C44(H44A,H44B,H44C), C39(H39A,H39B,H39C), C42(H42A,H42B,H42C), C38(H38A,H38B,
 H38C), C43(H43A,H43B,H43C), C40(H40A,H40B,H40C)
;
_shelx_res_checksum              95046
_shelx_hkl_checksum              3304
_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 1.121
_oxdiff_exptl_absorpt_empirical_full_min 0.886