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_1575471
_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         'I, C9 H14 N O3'
_chemical_formula_sum            'C9 H14 I N O3'
_chemical_formula_weight         311.11
_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   geom
_audit_creation_date             2025-02-05
_audit_creation_method
;
Olex2 1.5
(compiled 2021.07.19 svn.r715e62df for OlexSys, GUI svn.r6380)
;
_audit_update_record
;
2025-04-08 deposited with the CCDC.	2025-08-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 98.5070(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   6.62750(10)
_cell_length_b                   11.30050(10)
_cell_length_c                   14.8296(2)
_cell_measurement_reflns_used    6627
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      78.3530
_cell_measurement_theta_min      4.9230
_cell_volume                     1098.43(2)
_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      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 7.41
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.969
_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    -60.00 -33.00   0.50    0.20    -- -106.00  61.00  90.00   54
  2  \w   -105.00 -67.00   0.50    0.20    -- -106.00  77.00 -30.00   76
  3  \w    -66.00 -33.00   0.50    0.20    -- -106.00  61.00 -60.00   66
  4  \w    -62.00 -35.00   0.50    0.20    -- -106.00  61.00-120.00   54
  5  \w    -70.00 -33.00   0.50    0.20    -- -106.00  61.00-150.00   74
  6  \w    -67.00 -34.00   0.50    0.20    -- -106.00  61.00-180.00   66
  7  \w    -71.00 -41.00   0.50    0.20    -- -106.00  61.00 -90.00   60
  8  \w    -71.00 -34.00   0.50    0.20    -- -106.00  61.00 150.00   74
  9  \w    -59.00 -33.00   0.50    0.20    -- -106.00  61.00  60.00   52
 10  \w    -71.00 -34.00   0.50    0.20    -- -106.00  61.00   0.00   74
 11  \w    -68.00 -36.00   0.50    0.20    -- -106.00  61.00 -30.00   64
 12  \w    -23.00  43.00   0.50    0.10    --   47.95 -38.00 -60.00  132
 13  \w    -25.00   0.00   0.50    0.10    --  -47.95  23.00-117.00   50
 14  \w    -26.00  -1.00   0.50    0.10    --   47.95 -19.00 -60.00   50
 15  \w    -26.00  21.00   0.50    0.10    --   47.95 -23.00  77.00   94
 16  \w     57.00 111.00   0.50    0.20    --  113.25-125.00  30.00  108
 17  \w     69.00  99.00   0.50    0.20    --  113.25 -95.00 -30.00   60
 18  \w    138.00 177.00   0.50    0.20    --  113.25  23.00-117.00   78
 19  \w    102.00 168.00   0.50    0.20    --  113.25  30.00-150.00  132
 20  \w    133.00 177.00   0.50    0.20    --  113.25  45.00 -60.00   88
 21  \w     48.00 122.00   0.50    0.10    --   47.95  23.00-117.00  148
 22  \w     74.00 104.00   0.50    0.20    --  113.25 -77.00  90.00   60
 23  \w     45.00  70.00   0.50    0.20    --  113.25 -61.00 150.00   50
 24  \w     46.00  72.00   0.50    0.20    --  113.25 -77.00  90.00   52
 25  \w     44.00  69.00   0.50    0.20    --  113.25 -61.00  60.00   50
 26  \w     42.00  67.00   0.50    0.20    --  113.25 -61.00   0.00   50
 27  \w    -91.00 -65.00   0.50    0.10    --  -47.95 -23.00  77.00   52
 28  \w    -90.00 -45.00   0.50    0.20    -- -106.00 125.00 -30.00   90
 29  \w   -134.00 -93.00   0.50    0.20    -- -106.00 -23.00  77.00   82
 30  \w   -114.00 -75.00   0.50    0.10    --  -47.95-125.00 -90.00   78
;
_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      0.2238730000
_diffrn_orient_matrix_UB_12      0.0392546000
_diffrn_orient_matrix_UB_13      0.0046980000
_diffrn_orient_matrix_UB_21      -0.0163356000
_diffrn_orient_matrix_UB_22      -0.0144042000
_diffrn_orient_matrix_UB_23      -0.1041621000
_diffrn_orient_matrix_UB_31      -0.0696088000
_diffrn_orient_matrix_UB_32      0.1297388000
_diffrn_orient_matrix_UB_33      -0.0128965000
_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  0.0241
_diffrn_reflns_av_unetI/netI     0.0203
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -8
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            8215
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.969
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.616
_diffrn_reflns_theta_min         4.941
_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    22.797
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.61741
_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 colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.881
_exptl_crystal_description       block
_exptl_crystal_F_000             608
_exptl_crystal_size_max          0.03
_exptl_crystal_size_mid          0.015
_exptl_crystal_size_min          0.015
_refine_diff_density_max         0.765
_refine_diff_density_min         -0.750
_refine_diff_density_rms         0.122
_refine_ls_extinction_coef       0.00161(13)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.091
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     133
_refine_ls_number_reflns         2322
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.091
_refine_ls_R_factor_all          0.0234
_refine_ls_R_factor_gt           0.0229
_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^)+(0.0416P)^2^+1.1904P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0639
_refine_ls_wR_factor_ref         0.0644
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2277
_reflns_number_total             2322
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03813h2.cif
_cod_data_source_block           6_100k_auto
_cod_depositor_comments
'Adding full bibliography for 1575468--1575476.cif.'
_cod_database_code               1575471
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C10 H10 O3 N1 I1'
_chemical_oxdiff_usercomment     'clear crystal'
_shelx_estimated_absorpt_t_max   0.726
_shelx_estimated_absorpt_t_min   0.548
_olex2_refinement_description
;
1.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B)
1.b Aromatic/amide H refined with riding coordinates:
 C2(H2A)
1.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C1(H1A,H1B,H1C)
1.d Idealised tetrahedral OH refined as rotating group:
 O2(H2), O3(H3), 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 1.369
_oxdiff_exptl_absorpt_empirical_full_min 0.795