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_1575473
_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         '1(I), C12 H18 N O3'
_chemical_formula_sum            'C12 H18 I N O3'
_chemical_formula_weight         351.17
_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             2025-01-22
_audit_creation_method
;
Olex2 1.5
(compiled 2021.07.19 svn.r715e62df for OlexSys, GUI svn.r6380)
;
_audit_update_record
;
2025-01-22 deposited with the CCDC.	2025-08-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90.739(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   14.3171(4)
_cell_length_b                   10.7495(4)
_cell_length_c                   8.9701(2)
_cell_measurement_reflns_used    5857
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      77.3110
_cell_measurement_theta_min      5.1790
_cell_volume                     1380.40(7)
_computing_cell_refinement       'CrysAlisPro 1.171.43.124a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.124a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.124a (Rigaku OD, 2024)'
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -69.00 -41.00   0.50    0.15    -- -106.00  61.00 120.00   56
  2  \w    -70.00 -34.00   0.50    0.15    -- -106.00  61.00  90.00   72
  3  \w    -70.00 -33.00   0.50    0.15    -- -106.00  61.00 -30.00   74
  4  \w    -66.00 -39.00   0.50    0.15    -- -106.00  61.00-120.00   54
  5  \w    -25.00  28.00   0.50    0.05    --  -47.95  19.00-120.00  106
  6  \w   -108.00 -52.00   0.50    0.15    -- -106.00 109.00   0.18  112
  7  \w    -97.00 -72.00   0.50    0.05    --  -47.95 158.00 -91.00   50
  8  \w   -105.00 -34.00   0.50    0.15    -- -106.00 158.00 -91.00  142
  9  \w    -79.00 -36.00   0.50    0.15    -- -106.00 125.00 -90.00   86
 10  \w    -83.00 -57.00   0.50    0.15    -- -106.00 145.00 -21.24   52
 11  \w   -126.00 -98.00   0.50    0.15    -- -106.00 145.00 -21.24   56
 12  \w   -126.00 -50.00   0.50    0.15    -- -106.00 145.00  70.33  152
 13  \w    -97.00 -72.00   0.50    0.15    -- -106.00 119.00 114.00   50
 14  \w   -108.00 -79.00   0.50    0.15    -- -106.00 109.00  94.17   58
 15  \w    -67.00 -37.00   0.50    0.15    -- -106.00 109.00  94.17   60
 16  \w    -73.00 -48.00   0.50    0.05    --  -47.95 119.00 114.00   50
 17  \w     59.00 106.00   0.50    0.15    --  113.25 -95.00  60.00   94
 18  \w     78.00 106.00   0.50    0.15    --  113.25-119.00  29.00   56
 19  \w     64.00  94.00   0.50    0.15    --  113.25 -95.00  30.00   60
 20  \w     64.00  89.00   0.50    0.15    --  113.25-158.00-124.00   50
 21  \w     79.00 104.00   0.50    0.15    --  113.25 -95.00-180.00   50
 22  \w     25.00  56.00   0.50    0.05    --   47.95  77.00-180.00   62
 23  \w     59.00 121.00   0.50    0.05    --   47.95  77.00-180.00  124
 24  \w    102.00 177.00   0.50    0.15    --  113.25  45.00  30.00  150
 25  \w    102.00 133.00   0.50    0.15    --  113.25  45.00  90.00   62
 26  \w    139.00 173.00   0.50    0.15    --  113.25  45.00  90.00   68
 27  \w    142.00 178.00   0.50    0.15    --  113.25  15.00 120.00   72
 28  \w    102.00 127.00   0.50    0.15    --  113.25  15.00 120.00   50
 29  \w     78.00 111.00   0.50    0.05    --   47.95 158.00 -91.00   66
 30  \w     83.00 109.00   0.50    0.15    --  113.25 158.00 -91.00   52
 31  \w     27.00  89.00   0.50    0.05    --   47.95-119.00  29.00  124
 32  \w   -117.00 -78.00   0.50    0.05    --  -47.95-125.00  90.00   78
 33  \w    -88.00 -62.00   0.50    0.05    --  -47.95-158.00-124.00   52
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_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      0.1023654000
_diffrn_orient_matrix_UB_12      -0.0443684000
_diffrn_orient_matrix_UB_13      -0.0026917000
_diffrn_orient_matrix_UB_21      -0.0334283000
_diffrn_orient_matrix_UB_22      -0.1349856000
_diffrn_orient_matrix_UB_23      -0.0227976000
_diffrn_orient_matrix_UB_31      0.0014713000
_diffrn_orient_matrix_UB_32      0.0187362000
_diffrn_orient_matrix_UB_33      -0.1700759000
_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  0.0731
_diffrn_reflns_av_unetI/netI     0.0642
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -10
_diffrn_reflns_number            10253
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        64.979
_diffrn_reflns_theta_max         64.979
_diffrn_reflns_theta_min         3.087
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    18.220
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.10058
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.124a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear whiteish colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   whiteish
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.690
_exptl_crystal_description       plate
_exptl_crystal_F_000             696
_exptl_crystal_size_max          0.129
_exptl_crystal_size_mid          0.102
_exptl_crystal_size_min          0.098
_refine_diff_density_max         2.090
_refine_diff_density_min         -1.225
_refine_diff_density_rms         0.208
_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     165
_refine_ls_number_reflns         2349
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.036
_refine_ls_R_factor_all          0.0651
_refine_ls_R_factor_gt           0.0617
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1060P)^2^+5.6018P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1620
_refine_ls_wR_factor_ref         0.1656
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2106
_reflns_number_total             2349
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03813h2.cif
_cod_data_source_block           1pym_mecn_auto
_cod_depositor_comments
'Adding full bibliography for 1575468--1575476.cif.'
_cod_database_code               1575473
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C H N O I'
_chemical_oxdiff_usercomment     'mecn, slow evap, rt'
_shelx_estimated_absorpt_t_max   0.268
_shelx_estimated_absorpt_t_min   0.202
_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. Uiso/Uaniso restraints and constraints
Uanis(I2) = Uanis(I1) = Uanis(I3)
3. Others
 Fixed Sof: I1(0.9) I2(0.05) I3(0.05)
4.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B)
4.b Aromatic/amide H refined with riding coordinates:
 C1(H1A)
4.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,H12C)
4.d Idealised tetrahedral OH refined as rotating group:
 O1(H1)
;
_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 4.067
_oxdiff_exptl_absorpt_empirical_full_min 0.520