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_1575470
_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, C7 H10 N'
_chemical_formula_sum            'C7 H10 I N'
_chemical_formula_weight         235.06
_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     iterative
_audit_creation_date             2025-01-31
_audit_creation_method
;
Olex2 1.5
(compiled 2021.07.19 svn.r715e62df for OlexSys, GUI svn.r6380)
;
_audit_update_record
;
2025-01-31 deposited with the CCDC.	2025-08-15 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 106.7085(19)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.09315(15)
_cell_length_b                   8.55139(12)
_cell_length_c                   11.5954(2)
_cell_measurement_reflns_used    4097
_cell_measurement_temperature    150.01(10)
_cell_measurement_theta_max      77.0360
_cell_measurement_theta_min      5.1000
_cell_volume                     863.58(3)
_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    'olex2.solve 1.5 (Bourhis et al., 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150.01(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 0.972
_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    -24.00  51.00   0.50    0.05    --   47.95 -63.00 -55.00  150
  2  \w     43.00  72.00   0.50    0.10    --  113.25 -63.00 -55.00   58
  3  \w     57.00 100.00   0.50    0.10    --  113.25 -77.00   0.00   86
  4  \w     42.00  71.00   0.50    0.10    --  113.25 -61.00  90.00   58
  5  \w     44.00  69.00   0.50    0.10    --  113.25 -61.00 120.00   50
  6  \w     43.00  68.00   0.50    0.10    --  113.25 -61.00 150.00   50
  7  \w     42.00  67.00   0.50    0.10    --  113.25 -61.00   0.00   50
  8  \w     43.00  70.00   0.50    0.10    --  113.25 -61.00 -30.00   54
  9  \w     44.00  69.00   0.50    0.10    --  113.25 -61.00-120.00   50
 10  \w     43.00  95.00   0.50    0.10    --  113.25 -95.00-120.00  104
 11  \w    101.00 168.00   0.50    0.10    --  113.25  45.00 -30.00  134
 12  \w    126.00 176.00   0.50    0.10    --  113.25  63.00  81.00  100
 13  \w    -41.00   1.00   0.50    0.05    --  -47.95  63.00  81.00   84
 14  \w     56.00 113.00   0.50    0.05    --   47.95  63.00  81.00  114
 15  \w    124.00 170.00   0.50    0.10    --  113.25  45.00  30.00   92
 16  \w    121.00 169.00   0.50    0.10    --  113.25  45.00   0.00   96
 17  \w    -23.00  28.00   0.50    0.05    --  -47.95  19.00-120.00  102
 18  \w    -63.00 -37.00   0.50    0.10    -- -106.00  61.00 -90.00   52
 19  \w    -68.00 -42.00   0.50    0.10    -- -106.00  61.00-150.00   52
 20  \w    -70.00 -45.00   0.50    0.10    -- -106.00  61.00 -60.00   50
 21  \w    -66.00 -40.00   0.50    0.10    -- -106.00  63.00  81.00   52
 22  \w   -161.00-110.00   0.50    0.10    -- -106.00 -15.00 150.00  102
 23  \w   -175.00-119.00   0.50    0.10    -- -106.00 -61.00  60.00  112
 24  \w   -177.00-108.00   0.50    0.10    -- -106.00 -63.00 -55.00  138
 25  \w   -118.00 -75.00   0.50    0.05    --  -47.95-125.00   0.00   86
 26  \w   -100.00 -75.00   0.50    0.05    --  -47.95 -63.00 -55.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_measurement_specimen_support 'MiTeGen micromount'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0700287000
_diffrn_orient_matrix_UB_12      0.1293843000
_diffrn_orient_matrix_UB_13      -0.0918404000
_diffrn_orient_matrix_UB_21      0.1586223000
_diffrn_orient_matrix_UB_22      0.0300510000
_diffrn_orient_matrix_UB_23      -0.0186966000
_diffrn_orient_matrix_UB_31      -0.0352208000
_diffrn_orient_matrix_UB_32      -0.1217016000
_diffrn_orient_matrix_UB_33      -0.1022457000
_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  0.0421
_diffrn_reflns_av_unetI/netI     0.0374
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.972
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       9
_diffrn_reflns_limit_k_min       -10
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            6192
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.972
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.438
_diffrn_reflns_theta_min         5.078
_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    28.490
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.28607
_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    1.808
_exptl_crystal_description       plate
_exptl_crystal_F_000             448
_exptl_crystal_size_max          0.078
_exptl_crystal_size_mid          0.055
_exptl_crystal_size_min          0.03
_refine_diff_density_max         1.304
_refine_diff_density_min         -1.927
_refine_diff_density_rms         0.157
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.839
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     83
_refine_ls_number_reflns         1822
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      0.839
_refine_ls_R_factor_all          0.0366
_refine_ls_R_factor_gt           0.0349
_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^)+(0.1000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0976
_refine_ls_wR_factor_ref         0.1012
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1690
_reflns_number_total             1822
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03813h2.cif
_cod_data_source_block           n-etpyi_auto
_cod_depositor_comments
'Adding full bibliography for 1575468--1575476.cif.'
_cod_database_code               1575470
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C20 H20 N I'
_chemical_oxdiff_usercomment     'blocks, transparent, MeCN, rt'
_shelx_estimated_absorpt_t_max   0.482
_shelx_estimated_absorpt_t_min   0.215
_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
2.a Secondary CH2 refined with riding coordinates:
 C6(H6A,H6B)
2.b Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C5(H5)
2.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C)
;
_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 2.455
_oxdiff_exptl_absorpt_empirical_full_min 0.651