Fast, efficient, narrowband room-temperature phosphorescence from metal-free 1,2-diketones: rational design and the mechanism.
Tani, Yosuke; Miyata, Kiyoshi; Ou, Erika; Oshima, Yuya; Komura, Mao; Terasaki, Morihisa; Kimura, Shuji; Ehara, Takumi; Kubo, Koki; Onda, Ken; Ogawa, Takuji; Chemical science 15 (2024) 10784–10793; doi:10.1039/d4sc02841d

data_1571785
_publ_section_title
;
 Fast, efficient, narrowband room-temperature phosphorescence from
 metal-free 1,2-diketones: rational design and the mechanism.
;
_journal_issue                   28
_journal_name_full               'Chemical science'
_journal_page_first              10784
_journal_page_last               10793
_journal_paper_doi               10.1039/d4sc02841d
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C34 H56 Br2 O2 S2 Si2'
_chemical_formula_sum            'C34 H56 Br2 O2 S2 Si2'
_chemical_formula_weight         776.90
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2g5zh4
_audit_creation_date             2023-06-14
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2023-06-14 deposited with the CCDC.	2024-06-03 downloaded from the CCDC.
;
_cell_angle_alpha                76.484(4)
_cell_angle_beta                 77.312(4)
_cell_angle_gamma                76.710(4)
_cell_formula_units_Z            1
_cell_length_a                   9.4163(4)
_cell_length_b                   10.5452(5)
_cell_length_c                   10.6006(5)
_cell_measurement_reflns_used    7628
_cell_measurement_temperature    123
_cell_measurement_theta_max      29.6940
_cell_measurement_theta_min      1.9960
_cell_volume                     980.61(8)
_computing_cell_refinement       'CrysAlisPro 1.171.40.75a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.40.75a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.40.75a (Rigaku OD, 2020)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      123.15
_diffrn_detector                 'Rigaku HyPix-6000 area detector'
_diffrn_detector_area_resol_mean 10.0
_diffrn_detector_type            'HPC area detector'
_diffrn_measured_fraction_theta_full 0.967
_diffrn_measured_fraction_theta_max 0.755
_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    -11.00  30.00   0.50    3.00    --   10.29 -99.00  60.00   82
  2  \w     14.00  61.00   0.50    3.00    --   10.29-119.00 110.00   94
  3  \w     33.00  82.00   0.50    3.00    --   10.29-156.00 -44.00   98
  4  \w    -11.00  50.00   0.50    3.00    --   10.29 -99.00-150.00  122
  5  \w     -8.00  34.00   0.50    3.00    --   10.29 -99.00 -30.00   84
  6  \w    -64.00  33.00   0.50    3.00    --   10.29 -57.00  90.00  194
  7  \w    -11.00  34.00   0.50    3.00    --   -5.05 -99.00   0.00   90
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB Synergy-R'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0098990000
_diffrn_orient_matrix_UB_12      0.0688948000
_diffrn_orient_matrix_UB_13      -0.0274402000
_diffrn_orient_matrix_UB_21      0.0050369000
_diffrn_orient_matrix_UB_22      0.0135898000
_diffrn_orient_matrix_UB_23      0.0611546000
_diffrn_orient_matrix_UB_31      0.0778288000
_diffrn_orient_matrix_UB_32      -0.0055100000
_diffrn_orient_matrix_UB_33      -0.0198280000
_diffrn_radiation_monochromator  'multi-layer mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0217
_diffrn_reflns_av_unetI/netI     0.0266
_diffrn_reflns_Laue_measured_fraction_full 0.967
_diffrn_reflns_Laue_measured_fraction_max 0.755
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            10427
_diffrn_reflns_point_group_measured_fraction_full 0.967
_diffrn_reflns_point_group_measured_fraction_max 0.755
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.775
_diffrn_reflns_theta_min         2.007
_diffrn_source                   'rotating anode X-ray generator'
_diffrn_source_type              PhotonJet-R
_exptl_absorpt_coefficient_mu    2.261
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64674
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.75a (Rigaku Oxford Diffraction, 2020)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.316
_exptl_crystal_description       block
_exptl_crystal_F_000             406
_exptl_crystal_preparation       'recrystallized from (TMS)2O,Luminescent'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: hexamethyldisiloxane'
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.15
_refine_diff_density_max         0.401
_refine_diff_density_min         -0.355
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.024
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     222
_refine_ls_number_reflns         4223
_refine_ls_number_restraints     5
_refine_ls_restrained_S_all      1.028
_refine_ls_R_factor_all          0.0292
_refine_ls_R_factor_gt           0.0254
_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^)+(0.0337P)^2^+0.4035P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0648
_refine_ls_wR_factor_ref         0.0667
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3861
_reflns_number_total             4223
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc02841d4.cif
_cod_data_source_block           1c
_cod_depositor_comments          'Adding full bibliography for 1571785.cif.'
_cod_database_code               1571785
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C34H56O2S2Si2Br2
_chemical_oxdiff_usercomment     'TMS2O 123K'
_shelx_estimated_absorpt_t_max   0.728
_shelx_estimated_absorpt_t_min   0.550
_reflns_odcompleteness_completeness 96.65
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     25.30
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C14-C15 \\sim C14-C15A
 with sigma of 0.02
 C15-C16 \\sim C15A-C16A
 with sigma of 0.02
 C15-C17 \\sim C15A-C17A
 with sigma of 0.04
 C16-C17 \\sim C16A-C17A
 with sigma of 0.02
 C14-C16 \\sim C14-C16A
 with sigma of 0.04
3. Others
 Sof(H14C)=Sof(H14D)=Sof(C17A)=Sof(H17D)=Sof(H17E)=Sof(H17F)=Sof(C16A)=
 Sof(H16C)=Sof(H16D)=Sof(C15A)=Sof(H15C)=Sof(H15D)=1-FVAR(1)
 Sof(H14A)=Sof(H14B)=Sof(C15)=Sof(H15A)=Sof(H15B)=Sof(C16)=Sof(H16A)=Sof(H16B)=
 Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=FVAR(1)
4.a Secondary CH2 refined with riding coordinates:
 C10(H10A,H10B), C6(H6A,H6B), C11(H11A,H11B), C7(H7A,H7B), C12(H12A,H12B),
 C14(H14A,H14B), C14(H14C,H14D), C8(H8A,H8B), C15(H15A,H15B), C16(H16A,H16B),
 C16A(H16C,H16D), C15A(H15C,H15D)
4.b Aromatic/amide H refined with riding coordinates:
 C4(H4)
4.c Idealised Me refined as rotating group:
 C9(H9A,H9B,H9C), C13(H13A,H13B,H13C), C17(H17A,H17B,H17C), C17A(H17D,H17E,H17F)
;
_shelx_res_checksum              76896
_shelx_hkl_checksum              81838
_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 1.631
_oxdiff_exptl_absorpt_empirical_full_min 0.592