Metal-free pyridinium salts with strong room-temperature phosphorescence and microsecond radiative lifetime.
Hakkarainen, Eetu; Lin, Hao-Cheng; Nechaev, Anton A.; Peshkov, Vsevolod A.; Eskelinen, Toni; Chang, Kai-Hsin; Liao, Tzu-Hao; Chen, Po-Yu; Koshevoy, Igor O.; Lin, Hao-Wu; Chou, Pi-Tai; Belyaev, Andrey; Chemical science 16 (2025) 17261–17267; doi:10.1039/d5sc03813h

data_1575475
_publ_section_title
;
 Metal-free pyridinium salts with strong room-temperature phosphorescence
 and microsecond radiative lifetime.
;
_journal_issue                   37
_journal_name_full               'Chemical science'
_journal_page_first              17261
_journal_page_last               17267
_journal_paper_doi               10.1039/d5sc03813h
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         '2(I), C30 H38 N2 O6'
_chemical_formula_sum            'C30 H38 I2 N2 O6'
_chemical_formula_weight         776.42
_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     iterative
_audit_creation_date             2024-11-04
_audit_creation_method
;
Olex2 1.5
(compiled 2021.07.19 svn.r715e62df for OlexSys, GUI svn.r6380)
;
_audit_update_record
;
2024-11-05 deposited with the CCDC.	2025-08-15 downloaded from the CCDC.
;
_cell_angle_alpha                105.939(2)
_cell_angle_beta                 93.744(2)
_cell_angle_gamma                94.0170(10)
_cell_formula_units_Z            2
_cell_length_a                   8.94630(10)
_cell_length_b                   12.7534(3)
_cell_length_c                   17.3129(3)
_cell_measurement_reflns_used    15508
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      77.9620
_cell_measurement_theta_min      2.6600
_cell_volume                     1887.35(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.89a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.985
_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    -53.00 -16.00   0.50    0.50    --  -87.58  57.00  30.00   74
  2  \w    -39.00 -14.00   0.50    0.50    --  -87.58  57.00 -30.00   50
  3  \w    -47.00 -13.00   0.50    0.50    --  -87.58  57.00 -90.00   68
  4  \w     -3.00  24.00   0.50    0.50    --  -51.70  19.00  60.00   54
  5  \w     -3.00  25.00   0.50    0.50    --  -51.70  19.00  30.00   56
  6  \w    -54.00 -13.00   0.50    0.50    --  -87.58  57.00-150.00   82
  7  \w     -3.00  25.00   0.50    0.50    --  -51.70  19.00-180.00   56
  8  \w     40.00 121.00   0.50    0.50    --   51.89-157.00-152.00  162
  9  \w     84.00 110.00   0.50    0.50    --  107.25-120.00-173.55   52
 10  \w     84.00 109.00   0.50    0.50    --  102.12-157.00-152.00   50
 11  \w     40.00  65.00   0.50    0.50    --  107.25-120.00-173.55   50
 12  \w     48.00  75.00   0.50    0.50    --  102.12-157.00-152.00   54
 13  \w     72.00 106.00   0.50    0.50    --  102.12 -99.00 -60.00   68
 14  \w     47.00  72.00   0.50    0.50    --  102.12-119.00   2.00   50
 15  \w     84.00 110.00   0.50    0.50    --  102.12-125.00 120.00   52
 16  \w     53.00  79.00   0.50    0.50    --  102.12-125.00 120.00   52
 17  \w     76.00 106.00   0.50    0.50    --  102.12 -99.00  60.00   60
 18  \w     33.00  58.00   0.50    0.50    --   51.89-119.00   2.00   50
 19  \w     77.00 106.00   0.50    0.50    --  102.12 -99.00  90.00   58
 20  \w     69.00 106.00   0.50    0.50    --  102.12 -99.00 -30.00   74
 21  \w     75.00 106.00   0.50    0.50    --  102.12 -99.00-120.00   62
 22  \w     50.00 106.00   0.50    0.50    --  102.12 -99.00-150.00  112
 23  \w     42.00 112.00   0.50    0.50    --  107.25 -87.00-122.16  140
 24  \w     99.00 126.00   0.50    0.50    --  107.25 -85.00 -53.36   54
 25  \w     44.00  74.00   0.50    0.50    --  107.25 -85.00 -53.36   60
 26  \w     42.00  68.00   0.50    0.50    --  107.25 -87.00  93.36   52
 27  \w     41.00  73.00   0.50    0.50    --  107.25 -85.00 123.06   64
 28  \w     42.00  90.00   0.50    0.50    --  107.25 -85.00 170.31   96
 29  \w     44.00  69.00   0.50    0.50    --  107.25 -83.00 172.70   50
 30  \w     98.00 125.00   0.50    0.50    --  107.25 -85.00 123.06   54
 31  \w    105.00 131.00   0.50    0.50    --  107.25 -84.00  25.49   52
 32  \w     53.00  78.00   0.50    0.50    --  107.25 -84.00  25.49   50
 33  \w     41.00  86.00   0.50    0.50    --  107.25 -83.00 -97.89   90
 34  \w     43.00  97.00   0.50    0.50    --  107.25 -83.00-163.39  108
 35  \w     25.00  50.00   0.50    0.50    --  102.12 -38.00-120.00   50
 36  \w     45.00  75.00   0.50    0.50    --  107.25 -79.00 -68.92   60
 37  \w     60.00  86.00   0.50    0.50    --  107.25 -79.00-109.44   52
 38  \w    102.00 128.00   0.50    0.50    --  107.25 -79.00-109.44   52
 39  \w     49.00  81.00   0.50    0.50    --  107.25 -77.00 -90.64   64
 40  \w     44.00  92.00   0.50    0.50    --  107.25 -78.00 -19.89   96
 41  \w     48.00  88.00   0.50    0.50    --  107.25 -77.00  33.75   80
 42  \w     56.00 106.00   0.50    0.50    --  107.25 -75.00  69.02  100
 43  \w     36.00  69.00   0.50    0.50    --  102.12 -77.00  60.00   66
 44  \w     38.00  64.00   0.50    0.50    --  107.25 -72.00  54.21   52
 45  \w     42.00  69.00   0.50    0.50    --  107.25 -77.00  93.35   54
 46  \w     42.00  74.00   0.50    0.50    --  107.25 -79.00 141.30   64
 47  \w     42.00  67.00   0.50    0.50    --  107.25 -76.00 107.59   50
 48  \w     45.00  99.00   0.50    0.50    --  107.25 -75.00 117.36  108
 49  \w     37.00  66.00   0.50    0.50    --  107.25 -69.00 -45.91   58
 50  \w     39.00  64.00   0.50    0.50    --  107.25 -68.00 -16.23   50
 51  \w     26.00  51.00   0.50    0.50    --  102.12 -38.00 120.00   50
 52  \w     57.00  82.00   0.50    0.50    --  107.25   3.00 109.69   50
 53  \w    106.00 131.00   0.50    0.50    --  107.25  71.00 164.09   50
 54  \w    150.00 175.00   0.50    0.50    --  107.25  71.00 164.09   50
 55  \w     94.00 121.00   0.50    0.50    --  102.12  38.00  30.00   54
 56  \w     65.00 149.00   0.50    0.50    --  107.25  18.00  50.67  168
 57  \w    144.00 175.00   0.50    0.50    --  102.12  38.00  30.00   62
 58  \w    127.00 170.00   0.50    0.50    --  107.25  16.00 -67.61   86
 59  \w    151.00 176.00   0.50    0.50    --  107.25  19.00-179.81   50
 60  \w     84.00 127.00   0.50    0.50    --  107.25  19.00-179.81   86
 61  \w     65.00 143.00   0.50    0.50    --  107.25  18.00-120.52  156
 62  \w     98.00 123.00   0.50    0.50    --  107.25  16.00 -67.61   50
 63  \w     76.00 101.00   0.50    0.50    --  107.25  16.00  23.00   50
 64  \w     70.00 167.00   0.50    0.50    --  107.25  16.00 -16.60  194
 65  \w    125.00 151.00   0.50    0.50    --  107.25  15.00 122.02   52
 66  \w    105.00 130.00   0.50    0.50    --  107.25  16.00 156.44   50
 67  \w     59.00  98.00   0.50    0.50    --  107.25  16.00 156.44   78
 68  \w     64.00  91.00   0.50    0.50    --  107.25  15.00 122.02   54
 69  \w     91.00 116.00   0.50    0.50    --  107.25  93.00 -16.12   50
 70  \w    120.00 146.00   0.50    0.50    --  102.12 119.00  87.00   52
 71  \w     84.00 116.00   0.50    0.50    --  102.12 125.00  60.00   64
 72  \w    141.00 166.00   0.50    0.50    --  107.25  93.00 -16.12   50
 73  \w     85.00 110.00   0.50    0.50    --  102.12 157.00-116.00   50
 74  \w     97.00 145.00   0.50    0.50    --  107.25 109.00-169.27   96
 75  \w    144.00 173.00   0.50    0.50    --  107.25 116.00-166.94   58
 76  \w     64.00  89.00   0.50    0.50    --   51.89 157.00-116.00   50
 77  \w   -102.00 -77.00   0.50    0.50    --  -51.70 157.00-116.00   50
 78  \w   -113.00 -81.00   0.50    0.50    --  -87.58 157.00-116.00   64
 79  \w    -74.00 -47.00   0.50    0.50    --  -87.58 119.00  87.00   54
 80  \w    -79.00 -54.00   0.50    0.50    --  -51.70 119.00  87.00   50
 81  \w   -164.00 -74.00   0.50    0.50    --  -87.58 -38.00  60.00  180
 82  \w   -133.00 -81.00   0.50    0.50    --  -87.58-119.00   2.00  104
 83  \w   -122.00 -80.00   0.50    0.50    --  -51.70-125.00 150.00   84
 84  \w   -126.00 -38.00   0.50    0.50    --  -51.70 -57.00 -90.00  176
 85  \w    -91.00 -63.00   0.50    0.50    --  -51.70-157.00-152.00   56
 86  \w   -112.00 -85.00   0.50    0.50    --  -87.58-157.00-152.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, HyPix-Arc 100'
_diffrn_measurement_method       '\w scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0318526000
_diffrn_orient_matrix_UB_12      -0.1036004000
_diffrn_orient_matrix_UB_13      -0.0650734000
_diffrn_orient_matrix_UB_21      -0.0238195000
_diffrn_orient_matrix_UB_22      0.0599134000
_diffrn_orient_matrix_UB_23      -0.0653039000
_diffrn_orient_matrix_UB_31      0.1686738000
_diffrn_orient_matrix_UB_32      0.0399115000
_diffrn_orient_matrix_UB_33      0.0114794000
_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  0.0946
_diffrn_reflns_av_unetI/netI     0.0606
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            42103
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.238
_diffrn_reflns_theta_min         3.847
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_type              'PhotonJet R (Cu) X-ray Source'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    13.383
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.682
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.89a (Rigaku Oxford Diffraction, 2023)
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            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.366
_exptl_crystal_description       block
_exptl_crystal_F_000             772
_exptl_crystal_size_max          0.301
_exptl_crystal_size_mid          0.031
_exptl_crystal_size_min          0.028
_refine_diff_density_max         3.022
_refine_diff_density_min         -1.096
_refine_diff_density_rms         0.153
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.094
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     374
_refine_ls_number_reflns         8064
_refine_ls_number_restraints     7
_refine_ls_restrained_S_all      1.094
_refine_ls_R_factor_all          0.0804
_refine_ls_R_factor_gt           0.0697
_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^)+(0.1251P)^2^+1.6552P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1966
_refine_ls_wR_factor_ref         0.2054
_reflns_Friedel_coverage         0.000
_reflns_number_gt                6419
_reflns_number_total             8064
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03813h2.cif
_cod_data_source_block           4
_cod_depositor_comments
'Adding full bibliography for 1575468--1575476.cif.'
_cod_database_code               1575475
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C40H40N2O4Cl3
_chemical_oxdiff_usercomment     'ether, methanol, chloroform at rt, gas-phase'
_shelx_estimated_absorpt_t_max   0.690
_shelx_estimated_absorpt_t_min   0.108
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All O(H) groups
2. Restrained distances
 H2-O2
 0.98 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(O1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(O1) = Uanis(C7)
4. Others
 Fixed Sof: I2(0.9) I2A(0.1)
5.a Riding coordinates:
 O1(H1A)
5.b Secondary CH2 refined with riding coordinates:
 C23(H23A,H23B), C19(H19A,H19B), C30(H30A,H30B), C8(H8A,H8B), C18(H18A,H18B),
 C7(H7A,H7B)
5.c Aromatic/amide H refined with riding coordinates:
 C12(H12), C25(H25), C28(H28), C29(H29), C26(H26), C1(H1)
5.d Idealised Me refined as rotating group:
 C17(H17A,H17B,H17C), C6(H6A,H6B,H6C), C10(H10A,H10B,H10C), C22(H22A,H22B,
 H22C), C21(H21A,H21B,H21C), C11(H11A,H11B,H11C)
;
_smtbx_masks_void_probe_radius   1.0
_smtbx_masks_void_truncation_radius 1.0
_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 3.331
_oxdiff_exptl_absorpt_empirical_full_min 0.391