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_1575469
_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_absolute_configuration ad
_chemical_formula_moiety         'I, C13 H20 N O3'
_chemical_formula_sum            'C13 H20 I N O3'
_chemical_formula_weight         365.20
_space_group_crystal_system      monoclinic
_space_group_IT_number           9
_space_group_name_Hall           'C -2yc'
_space_group_name_H-M_alt        'C 1 c 1'
_atom_sites_solution_hydrogens   geom
_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                 92.256(2)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   8.5894(2)
_cell_length_b                   16.0241(4)
_cell_length_c                   10.5135(3)
_cell_measurement_reflns_used    5119
_cell_measurement_temperature    120.01(10)
_cell_measurement_theta_max      31.2750
_cell_measurement_theta_min      2.6910
_cell_volume                     1445.93(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.80a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.80a (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      120.01(10)
_diffrn_detector                 HPAD
_diffrn_detector_area_resol_mean 7.41
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.794
_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    -36.00 -10.00   0.50    4.00    --    0.71 -78.00  85.00   52
  2  \w    -23.00  24.00   0.50    4.00    --    0.71 -99.00  30.00   94
  3  \w    -11.00  30.00   0.50    4.00    --    0.71 -99.00-150.00   82
  4  \w    -18.00  28.00   0.50    4.00    --    0.71 -99.00  60.00   92
  5  \w    -13.00  30.00   0.50    4.00    --    0.71 -99.00 -90.00   86
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dualflex, 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      -0.0273143000
_diffrn_orient_matrix_UB_12      0.0316254000
_diffrn_orient_matrix_UB_13      -0.0425541000
_diffrn_orient_matrix_UB_21      -0.0737343000
_diffrn_orient_matrix_UB_22      -0.0198735000
_diffrn_orient_matrix_UB_23      -0.0051770000
_diffrn_orient_matrix_UB_31      -0.0253490000
_diffrn_orient_matrix_UB_32      0.0237575000
_diffrn_orient_matrix_UB_33      0.0521872000
_diffrn_radiation_monochromator  'multilayer optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0238
_diffrn_reflns_av_unetI/netI     0.0306
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.794
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            6163
_diffrn_reflns_point_group_measured_fraction_full 0.823
_diffrn_reflns_point_group_measured_fraction_max 0.607
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         31.422
_diffrn_reflns_theta_min         2.692
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_current           1.4
_diffrn_source_power             0.07
_diffrn_source_type              'SuperNova (Mo) X-ray Source'
_diffrn_source_voltage           50.0
_exptl_absorpt_coefficient_mu    2.216
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  1.00000
_exptl_absorpt_correction_type   sphere
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.80a (Rigaku Oxford Diffraction, 2023)
Spherical absorption correction
using equivalent radius and absorption coefficient.
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.678
_exptl_crystal_description       block
_exptl_crystal_F_000             728
_exptl_crystal_size_max          0.101
_exptl_crystal_size_mid          0.099
_exptl_crystal_size_min          0.076
_exptl_crystal_size_rad          0.400
_refine_diff_density_max         0.358
_refine_diff_density_min         -0.334
_refine_diff_density_rms         0.067
_refine_ls_abs_structure_details
;
 Flack x determined using 949 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.027(18)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.043
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     168
_refine_ls_number_reflns         2913
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0188
_refine_ls_R_factor_gt           0.0181
_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^)+(0.0185P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0414
_refine_ls_wR_factor_ref         0.0419
_reflns_Friedel_coverage         0.525
_reflns_Friedel_fraction_full    0.647
_reflns_Friedel_fraction_max     0.419
_reflns_number_gt                2834
_reflns_number_total             2913
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03813h2.cif
_cod_data_source_block           2
_cod_depositor_comments
'Adding full bibliography for 1575468--1575476.cif.'
_cod_database_code               1575469
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C13H20INO3
_chemical_oxdiff_usercomment     'gp vd, rt, dcm-et2o'
_shelx_estimated_absorpt_t_max   0.850
_shelx_estimated_absorpt_t_min   0.807
_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), C8(H8A,H8B), C12(H12A,H12B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1A)
2.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C13(H13A,H13B,H13C)
2.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 1.128
_oxdiff_exptl_absorpt_empirical_full_min 0.926