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_1575476
_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         '4(I), 2(C H2 Cl2), 4(C18 H21 N O3)'
_chemical_formula_sum            'C74 H88 Cl4 I4 N4 O12'
_chemical_formula_weight         1874.88
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 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                90
_cell_angle_beta                 104.7932(9)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   15.38142(13)
_cell_length_b                   9.39589(8)
_cell_length_c                   27.9600(2)
_cell_measurement_reflns_used    29867
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      78.3610
_cell_measurement_theta_min      3.2390
_cell_volume                     3906.90(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 7.41
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.993
_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    -51.00 -14.00   0.50    0.16    --  -87.59  57.00 150.00   74
  2  \w    -53.00 -26.00   0.50    0.16    --  -87.59  57.00 120.00   54
  3  \w    -11.00  22.00   0.50    0.16    --  -51.79  29.00  21.00   66
  4  \w    -51.00 -15.00   0.50    0.16    --  -87.59  57.00   0.00   72
  5  \w   -104.00 -78.00   0.50    0.16    --  -87.59 -29.00-138.00   52
  6  \w   -129.00 -35.00   0.50    0.16    --  -51.79 -29.00-138.00  188
  7  \w   -156.00-127.00   0.50    0.16    --  -87.59 -29.00-138.00   58
  8  \w   -113.00 -88.00   0.50    0.16    --  -87.59 -99.00 150.00   50
  9  \w   -153.00-117.00   0.50    0.16    --  -87.59 -99.00 150.00   72
 10  \w    -23.00  28.00   0.50    0.16    --   52.04 -19.00  60.00  102
 11  \w     57.00  82.00   0.50    0.16    --  107.25 -77.00  84.47   50
 12  \w     42.00 100.00   0.50    0.16    --  107.25 -74.00 -21.75  116
 13  \w     49.00  95.00   0.50    0.16    --  107.25 -78.00-149.59   92
 14  \w     46.00  89.00   0.50    0.16    --  107.25 -73.00  29.54   86
 15  \w     40.00  65.00   0.50    0.16    --  107.25 -71.00 114.86   50
 16  \w     51.00  99.00   0.50    0.16    --  107.25 -71.00  52.26   96
 17  \w     46.00  95.00   0.50    0.16    --  107.25 -70.00  -9.76   98
 18  \w     53.00  78.00   0.50    0.16    --  107.25 -71.00 -58.77   50
 19  \w     38.00  90.00   0.50    0.16    --  107.25 -69.00-128.22  104
 20  \w     44.00  82.00   0.50    0.16    --  107.25 -65.00 -50.42   76
 21  \w     35.00  60.00   0.50    0.16    --  107.25 -65.00 -95.19   50
 22  \w     54.00  97.00   0.50    0.16    --  107.25 -67.00  74.59   86
 23  \w     34.00  71.00   0.50    0.16    --  102.09 -57.00 120.00   74
 24  \w     40.00  89.00   0.50    0.16    --  107.25 -63.00 123.97   98
 25  \w     32.00  58.00   0.50    0.16    --  107.25 -49.00  49.09   52
 26  \w     39.00  65.00   0.50    0.16    --  107.25 -56.00 -82.16   52
 27  \w     25.00  50.00   0.50    0.16    --  102.09 -38.00 -90.00   50
 28  \w     25.00  50.00   0.50    0.16    --  102.09 -38.00-180.00   50
 29  \w     26.00  51.00   0.50    0.16    --  102.09 -38.00-120.00   50
 30  \w     25.00  50.00   0.50    0.16    --  102.09 -38.00   0.00   50
 31  \w    -18.00   7.00   0.50    0.16    --   52.04 -29.00-138.00   50
 32  \w     25.00  50.00   0.50    0.16    --  102.09 -38.00  30.00   50
 33  \w     83.00 143.00   0.50    0.16    --  107.25 121.00 -34.94  120
 34  \w    151.00 176.00   0.50    0.16    --  107.25 121.00 -34.94   50
 35  \w     99.00 124.00   0.50    0.16    --  107.25  68.00 102.52   50
 36  \w    134.00 171.00   0.50    0.16    --  107.25  68.00 102.52   74
 37  \w    125.00 175.00   0.50    0.16    --  107.25  57.00  35.78  100
 38  \w    151.00 176.00   0.50    0.16    --  102.09  29.00  21.00   50
 39  \w    149.00 176.00   0.50    0.16    --  107.25  46.00 -41.40   54
 40  \w    106.00 132.00   0.50    0.16    --  107.25  46.00 -41.40   52
 41  \w     88.00 133.00   0.50    0.16    --  102.09  29.00  21.00   90
 42  \w    144.00 170.00   0.50    0.16    --  107.25  16.00  31.43   52
 43  \w     89.00 115.00   0.50    0.16    --   52.04  29.00  21.00   52
 44  \w     39.00  75.00   0.50    0.16    --   52.04  29.00  21.00   72
 45  \w     73.00 124.00   0.50    0.16    --  107.25  16.00  31.43  102
 46  \w    124.00 150.00   0.50    0.16    --  107.25   6.00 -35.08   52
 47  \w     55.00  80.00   0.50    0.16    --  107.25   6.00 -35.08   50
 48  \w     92.00 133.00   0.50    0.16    --  107.25 -81.00-125.48   82
 49  \w    112.00 137.00   0.50    0.16    --  107.25 -86.00 -83.09   50
 50  \w     47.00  73.00   0.50    0.16    --  107.25 -86.00 -83.09   52
 51  \w     45.00  71.00   0.50    0.16    --  107.25 -81.00-125.48   52
 52  \w     37.00  74.00   0.50    0.16    --  102.09 -99.00   0.00   74
 53  \w     78.00 106.00   0.50    0.16    --  102.09 -99.00   0.00   56
 54  \w     51.00 102.00   0.50    0.16    --  107.25 -93.00 143.38  102
;
_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      0.0077690000
_diffrn_orient_matrix_UB_12      -0.0327648000
_diffrn_orient_matrix_UB_13      -0.0527542000
_diffrn_orient_matrix_UB_21      -0.0969128000
_diffrn_orient_matrix_UB_22      0.0532545000
_diffrn_orient_matrix_UB_23      -0.0212324000
_diffrn_orient_matrix_UB_31      0.0357005000
_diffrn_orient_matrix_UB_32      0.1515577000
_diffrn_orient_matrix_UB_33      -0.0039355000
_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  0.0434
_diffrn_reflns_av_unetI/netI     0.0253
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -35
_diffrn_reflns_number            55764
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.176
_diffrn_reflns_theta_min         3.004
_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    14.273
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.29386
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.89a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.594
_exptl_crystal_description       needle
_exptl_crystal_F_000             1872
_exptl_crystal_size_max          0.076
_exptl_crystal_size_mid          0.034
_exptl_crystal_size_min          0.021
_refine_diff_density_max         1.700
_refine_diff_density_min         -1.153
_refine_diff_density_rms         0.116
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     453
_refine_ls_number_reflns         8382
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.026
_refine_ls_R_factor_all          0.0419
_refine_ls_R_factor_gt           0.0375
_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^)+(0.0572P)^2^+10.1955P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0995
_refine_ls_wR_factor_ref         0.1033
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7561
_reflns_number_total             8382
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03813h2.cif
_cod_data_source_block           3
_cod_depositor_comments
'Adding full bibliography for 1575468--1575476.cif.'
_cod_database_code               1575476
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C20 H20 N2 I O4 Cl2'
_chemical_oxdiff_usercomment     'DCM-Et2O, RT, gp'
_shelx_estimated_absorpt_t_max   0.754
_shelx_estimated_absorpt_t_min   0.410
_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.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C12(H12A,H12B), C26(H26A,H26B), C30(H30A,H30B), C37(H37A,H37B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1A), C8(H8), C14(H14), C15(H15), C16(H16), C17(H17), C18(H18), C19(H19),
 C25(H25), C32(H32), C33(H33), C34(H34), C35(H35), C36(H36)
2.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C24(H24A,H24B,
 H24C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C)
2.d Idealised tetrahedral OH refined as rotating group:
 O4(H4)
;
_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 2.956
_oxdiff_exptl_absorpt_empirical_full_min 0.666