Oxidation reduces spin-orbital coupling to achieve robust fluorescent emission in halogen substituted dithieno[3,2-b:2′,3′-d]thiophene
Liu, Huimin; Zhuang, Zeyan; Hou, Yawen; Zhu, Yujiao; Xu, Ruofeng; Chen, Bin; Hu, Rong; Zhao, Zujin; Physical Chemistry Chemical Physics  (2025) –; doi:10.1039/D5CP01121C

data_7250564
_publ_section_title
;
 Oxidation reduces spin-orbital coupling to achieve robust fluorescent
 emission in halogen substituted
 dithieno[3,2-b:2&#x2032;,3&#x2032;-d]thiophene
;
_journal_name_full               'Physical Chemistry Chemical Physics'
_journal_paper_doi               10.1039/D5CP01121C
_journal_year                    2025
_chemical_formula_moiety         '0.286(C8 H4 O2 S3)'
_chemical_formula_sum            'C2.29 H1.14 O0.57 S0.86'
_chemical_formula_weight         65.23
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-C 2yc'
_space_group_name_H-M_alt        'C 1 2/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2024-01-10
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-08-21 deposited with the CCDC.	2025-06-17 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.31(3)
_cell_angle_gamma                90
_cell_formula_units_Z            14
_cell_length_a                   9.756(2)
_cell_length_b                   12.219(2)
_cell_length_c                   7.5175(15)
_cell_measurement_reflns_used    4193
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      27.5
_cell_measurement_theta_min      3.5
_cell_volume                     875.5(3)
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS  (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_diffrn_measurement_device_type  'Bruker P4'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0569
_diffrn_reflns_av_unetI/netI     0.0506
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -8
_diffrn_reflns_number            3495
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        25.015
_diffrn_reflns_theta_max         25.015
_diffrn_reflns_theta_min         3.335
_exptl_absorpt_coefficient_mu    0.802
_exptl_absorpt_correction_T_max  0.812
_exptl_absorpt_correction_T_min  0.723
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   'ABSCOR (Higashi, 1995)'
_exptl_crystal_colour            yellow
_exptl_crystal_density_diffrn    1.732
_exptl_crystal_description       block
_exptl_crystal_F_000             464
_exptl_crystal_size_max          0.588
_exptl_crystal_size_mid          0.376
_exptl_crystal_size_min          0.087
_refine_diff_density_max         0.380
_refine_diff_density_min         -0.345
_refine_diff_density_rms         0.062
_refine_ls_extinction_coef       0.009(3)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2018/3 (Sheldrick 2018)'
_refine_ls_goodness_of_fit_ref   1.090
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     61
_refine_ls_number_reflns         773
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.090
_refine_ls_R_factor_all          0.0354
_refine_ls_R_factor_gt           0.0334
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0512P)^2^+0.5716P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0936
_refine_ls_wR_factor_ref         0.0966
_reflns_Friedel_coverage         0.000
_reflns_number_gt                703
_reflns_number_total             773
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5cp01121c2.cif
_cod_data_source_block           tref_CCDC2
_cod_database_code               7250564
_shelx_shelxl_version_number     2018/3
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4)
;
_shelx_res_checksum              24830
_olex2_submission_special_instructions 'No special instructions were received'