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_1575472
_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         'Br, C11 H16 N O3'
_chemical_formula_sum            'C11 H16 Br N O3'
_chemical_formula_weight         290.16
_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             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                 99.3750(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.27720(10)
_cell_length_b                   16.3448(2)
_cell_length_c                   7.94350(10)
_cell_measurement_reflns_used    6505
_cell_measurement_temperature    120.00(10)
_cell_measurement_theta_max      75.5710
_cell_measurement_theta_min      4.8370
_cell_volume                     1188.42(2)
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      120.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 100'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.987
_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     32.00  58.00   0.50    0.05    --  102.09-125.00-120.00   52
  2  \w     81.00 106.00   0.50    0.05    --  102.09-125.00-120.00   50
  3  \w     66.00 104.00   0.50    0.05    --  102.09 -99.00 -60.00   76
  4  \w     36.00  61.00   0.50    0.05    --  102.09 -99.00 -60.00   50
  5  \w     67.00 106.00   0.50    0.05    --  102.09 -99.00   0.00   78
  6  \w     55.00 105.00   0.50    0.05    --  102.09 -99.00  30.00  100
  7  \w     81.00 106.00   0.50    0.05    --  102.09 -99.00  60.00   50
  8  \w     42.00  67.00   0.50    0.05    --  102.09 -99.00 150.00   50
  9  \w     35.00  77.00   0.50    0.05    --   52.04 -77.00 120.00   84
 10  \w     26.00  51.00   0.50    0.05    --  102.09 -38.00 120.00   50
 11  \w     39.00  78.00   0.50    0.05    --  102.09 -57.00 120.00   78
 12  \w      3.00  29.00   0.50    0.05    --   52.04 -77.00 120.00   52
 13  \w     28.00  75.00   0.50    0.05    --  102.09 -57.00  30.00   94
 14  \w     25.00  50.00   0.50    0.05    --  102.09 -38.00  30.00   50
 15  \w     25.00  50.00   0.50    0.05    --  102.09 -38.00   0.00   50
 16  \w     25.00  50.00   0.50    0.05    --  102.09 -38.00  60.00   50
 17  \w    -23.00   2.00   0.50    0.05    --   52.04  -9.00 156.00   50
 18  \w     26.00  52.00   0.50    0.05    --  102.09 -38.00 -30.00   52
 19  \w     28.00  77.00   0.50    0.05    --  102.09 -57.00 -90.00   98
 20  \w     26.00  51.00   0.50    0.05    --  102.09 -38.00 -90.00   50
 21  \w     37.00 113.00   0.50    0.05    --  102.09   9.00 -29.00  152
 22  \w    126.00 152.00   0.50    0.05    --  102.09   9.00 -29.00   52
 23  \w     82.00 114.00   0.50    0.05    --   52.04   9.00 -29.00   64
 24  \w     48.00  80.00   0.50    0.05    --   52.04   9.00 -29.00   64
 25  \w     17.00  44.00   0.50    0.05    --   52.04   9.00 -29.00   54
 26  \w    -53.00   1.00   0.50    0.05    --  -51.79  57.00  60.00  108
 27  \w    -44.00  11.00   0.50    0.05    --  -51.79  -9.00 156.00  110
 28  \w    -54.00 -21.00   0.50    0.05    --  -87.59  77.00 150.00   66
 29  \w   -108.00 -71.00   0.50    0.05    --  -87.59  77.00 150.00   74
 30  \w   -103.00 -41.00   0.50    0.05    --  -87.59  -9.00 156.00  124
 31  \w   -160.00-108.00   0.50    0.05    --  -87.59  -9.00 156.00  104
;
_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      -0.1602847000
_diffrn_orient_matrix_UB_12      0.0051886000
_diffrn_orient_matrix_UB_13      -0.0887567000
_diffrn_orient_matrix_UB_21      -0.0493361000
_diffrn_orient_matrix_UB_22      0.0102777000
_diffrn_orient_matrix_UB_23      0.1748149000
_diffrn_orient_matrix_UB_31      0.0142880000
_diffrn_orient_matrix_UB_32      0.0935444000
_diffrn_orient_matrix_UB_33      -0.0142366000
_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  0.0293
_diffrn_reflns_av_unetI/netI     0.0259
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -7
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            10040
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.520
_diffrn_reflns_theta_min         4.831
_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    4.673
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.75151
_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            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.622
_exptl_crystal_description       plate
_exptl_crystal_F_000             592
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.03
_refine_diff_density_max         0.643
_refine_diff_density_min         -0.336
_refine_diff_density_rms         0.067
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     149
_refine_ls_number_reflns         2456
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0278
_refine_ls_R_factor_gt           0.0248
_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^)+(0.0362P)^2^+0.4053P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0642
_refine_ls_wR_factor_ref         0.0657
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2234
_reflns_number_total             2456
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03813h2.cif
_cod_data_source_block           5
_cod_depositor_comments
'Adding full bibliography for 1575468--1575476.cif.'
_cod_database_code               1575472
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_usercomment     'meoh recryst'
_shelx_estimated_absorpt_t_max   0.873
_shelx_estimated_absorpt_t_min   0.487
_olex2_refinement_description
;
1.a Secondary CH2 refined with riding coordinates:
 C7(H7A,H7B), C8(H8A,H8B)
1.b Aromatic/amide H refined with riding coordinates:
 N1(H1A), C1(H1B)
1.c Idealised Me refined as rotating group:
 C6(H6A,H6B,H6C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C)
1.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 1.311
_oxdiff_exptl_absorpt_empirical_full_min 0.802