Regulation and Mechanisms of Full-Visible-Spectrum Emission in Solid and Liquid States for D-π-A Cyanobenzene-Phenothiazine Fluorescent Molecules
Li, Wenhao; Niu, Mengyao; Zhu, Yi-Yun; Zhang, Man; Gao, Haoyu; Zhang, Xin-Chao; Yang, Bo; Wei, Donghui; Chen, Xuenian; Chemical Science  (2025) –; doi:10.1039/D5SC06095H

data_1576394
_publ_section_title
;
 Regulation and Mechanisms of Full-Visible-Spectrum Emission in Solid and
 Liquid States for D-\p-A Cyanobenzene-Phenothiazine Fluorescent Molecules
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D5SC06095H
_journal_year                    2025
_chemical_formula_moiety         '2(C26 H15 N3 S), C H2 Cl2'
_chemical_formula_sum            'C53 H32 Cl2 N6 S2'
_chemical_formula_weight         887.86
_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             2024-03-25
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2025-07-21 deposited with the CCDC.	2025-12-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 116.946(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   25.4166(5)
_cell_length_b                   23.4191(3)
_cell_length_c                   8.12028(19)
_cell_measurement_reflns_used    6745
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      69.9800
_cell_measurement_theta_min      3.7550
_cell_volume                     4308.72(18)
_computing_cell_refinement       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.81a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      293(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2312
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 1.000
_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    -79.00   9.00   1.00    2.00    --  -33.50 113.00 -46.00   88
  2  \w     54.00  81.00   1.00    2.00    --   36.47-113.00-138.00   27
  3  \w     50.00  75.00   1.00   10.00    --  108.00-113.00-138.00   25
  4  \w    103.00 170.00   1.00   10.00    --  108.00 113.00 -46.00   67
  5  \w    -42.00 -17.00   1.00    1.25    --    0.00 113.00 -46.00   25
  6  \w    -61.00 -12.00   1.00    2.00    --  -33.50 -37.00-180.00   49
  7  \w   -103.00 -13.00   1.00    2.00    --  -33.50 -37.00  90.00   90
  8  \w    -55.00  -5.00   1.00    2.00    --  -33.50  37.00 -90.00   50
  9  \w   -105.00 -42.00   1.00    2.00    --  -33.50 178.00-150.00   63
 10  \w   -104.00 -76.00   1.00    2.00    --  -33.50 -37.00-180.00   28
 11  \w     12.00  37.00   1.00    2.00    --  -33.50  37.00 -90.00   25
 12  \w    -96.00 -40.00   1.00    2.00    --  -33.50 178.00 -60.00   56
 13  \w      2.00  34.00   1.00    2.00    --   36.47  87.00 119.13   32
 14  \w     83.00 109.00   1.00    2.00    --   36.47 178.00 -90.00   26
 15  \w     35.00  62.00   1.00    2.00    --   36.47  57.00 120.00   27
 16  \w     76.00 109.00   1.00   10.00    --  108.00-111.00 -60.00   33
 17  \w     97.00 178.00   1.00   10.00    --  108.00  45.00 150.00   81
 18  \w     41.00  96.00   1.00   10.00    --  108.00 -45.00   0.00   55
 19  \w    105.00 131.00   1.00   10.00    --  108.00 111.00-150.00   26
 20  \w     80.00 106.00   1.00   10.00    --  108.00-111.00  90.00   26
 21  \w     46.00 127.00   1.00   10.00    --  108.00 -61.00-120.00   81
 22  \w     46.00 107.00   1.00   10.00    --  108.00-111.00-180.00   61
 23  \w    147.00 173.00   1.00   10.00    --  108.00  77.00 -60.00   26
 24  \w    112.00 138.00   1.00   10.00    --  108.00  77.00 -60.00   26
 25  \w     41.00  85.00   1.00   10.00    --  108.00 -94.00-120.00   44
 26  \w     40.00 131.00   1.00   10.00    --  108.00 -30.00-180.00   91
 27  \w    101.00 161.00   1.00   10.00    --  108.00  77.00   0.00   60
 28  \w     74.00 100.00   1.00   10.00    --  108.00-111.00   0.00   26
 29  \w     40.00  65.00   1.00   10.00    --  108.00-111.00   0.00   25
 30  \w     99.00 126.00   1.00   10.00    --  108.00 -45.00   0.00   27
 31  \w     41.00 132.00   1.00   10.00    --  108.00 -77.00   0.00   91
 32  \w    107.00 133.00   1.00   10.00    --  108.00 111.00-180.00   26
 33  \w     37.00 142.00   1.00   10.00    --  108.00 -15.00 -30.00  105
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Xcalibur, Eos, Gemini'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0075897000
_diffrn_orient_matrix_UB_12      -0.0119718000
_diffrn_orient_matrix_UB_13      -0.1960623000
_diffrn_orient_matrix_UB_21      0.0564043500
_diffrn_orient_matrix_UB_22      -0.0367620500
_diffrn_orient_matrix_UB_23      0.0817682000
_diffrn_orient_matrix_UB_31      -0.0372186500
_diffrn_orient_matrix_UB_32      -0.0532360500
_diffrn_orient_matrix_UB_33      -0.0123597000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0289
_diffrn_reflns_av_unetI/netI     0.0244
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -30
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -27
_diffrn_reflns_limit_l_max       9
_diffrn_reflns_limit_l_min       -9
_diffrn_reflns_number            14883
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.078
_diffrn_reflns_theta_max         67.078
_diffrn_reflns_theta_min         3.775
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.622
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.94614
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.81a (Rigaku Oxford Diffraction, 2023)
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    1.369
_exptl_crystal_description       block
_exptl_crystal_F_000             1832
_exptl_crystal_size_max          0.16
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.09
_refine_diff_density_max         0.616
_refine_diff_density_min         -0.652
_refine_diff_density_rms         0.057
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.086
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     285
_refine_ls_number_reflns         3856
_refine_ls_number_restraints     1
_refine_ls_restrained_S_all      1.095
_refine_ls_R_factor_all          0.0718
_refine_ls_R_factor_gt           0.0625
_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^)+(0.0965P)^2^+3.3071P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1721
_refine_ls_wR_factor_ref         0.1825
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3191
_reflns_number_total             3856
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06095h2.cif
_cod_data_source_block           20240398_auto
_cod_original_cell_volume        4308.69(17)
_cod_database_code               1576394
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C20H20N4O4S4
_shelx_estimated_absorpt_t_max   0.798
_shelx_estimated_absorpt_t_min   0.679
_reflns_odcompleteness_completeness 99.97
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Restrained distances
 Cl1-C27
 1.75 with sigma of 0.02
3. Others
 Fixed Sof: H27A(0.5) H27B(0.5)
4.a Secondary CH2 refined with riding coordinates:
 C27(H27A,H27B)
4.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C9(H9), C10(H10), C11(H11), C12(H12),
 C14(H14), C15(H15), C17(H17), C18(H18), C21(H21), C23(H23), C24(H24)
;
_shelx_res_checksum              52213
_shelx_hkl_checksum              77889
_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 1.151
_oxdiff_exptl_absorpt_empirical_full_min 0.911