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_1576392
_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         'C31 H19 N3 S2'
_chemical_formula_sum            'C31 H19 N3 S2'
_chemical_formula_weight         497.61
_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     direct
_audit_creation_date             2024-01-10
_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                 98.6578(15)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.45379(16)
_cell_length_b                   14.6325(3)
_cell_length_c                   15.6043(2)
_cell_measurement_reflns_used    3976
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      70.1340
_cell_measurement_theta_min      4.1460
_cell_volume                     2359.71(7)
_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    -56.00  37.00   1.00    1.00    --  -33.50  37.00  30.00   93
  2  \w   -102.00 -15.00   1.00    1.00    --  -33.50 -57.00 120.00   87
  3  \w    -42.00   4.00   1.00    1.00    --  -33.50 -19.00  90.00   46
  4  \w   -100.00 -74.00   1.00    1.00    --  -33.50 -19.00  90.00   26
  5  \w    -59.00  36.00   1.00    1.00    --  -33.50  77.00  90.00   95
  6  \w     71.00  97.00   1.00    1.00    --   36.47 178.00-150.00   26
  7  \w     53.00 118.00   1.00    3.00    --  108.00 -45.00-120.00   65
  8  \w    108.00 171.00   1.00    3.00    --  108.00  45.00 120.00   63
  9  \w    104.00 177.00   1.00    3.00    --  108.00  77.00 150.00   73
 10  \w     40.00 128.00   1.00    3.00    --  108.00 -45.00 120.00   88
 11  \w     91.00 177.00   1.00    3.00    --  108.00  45.00  60.00   86
 12  \w     40.00  86.00   1.00    3.00    --  108.00 -94.00-120.00   46
 13  \w     94.00 144.00   1.00    3.00    --  108.00  45.00-150.00   50
;
_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      -0.0484661000
_diffrn_orient_matrix_UB_12      -0.0679354000
_diffrn_orient_matrix_UB_13      -0.0731955000
_diffrn_orient_matrix_UB_21      -0.1323238000
_diffrn_orient_matrix_UB_22      -0.0045737000
_diffrn_orient_matrix_UB_23      0.0318781000
_diffrn_orient_matrix_UB_31      -0.0484721000
_diffrn_orient_matrix_UB_32      0.0802915000
_diffrn_orient_matrix_UB_33      -0.0600526000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0291
_diffrn_reflns_av_unetI/netI     0.0409
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 1.000
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            8434
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 1.000
_diffrn_reflns_theta_full        67.079
_diffrn_reflns_theta_max         67.079
_diffrn_reflns_theta_min         4.164
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.247
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.80899
_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    1.401
_exptl_crystal_description       block
_exptl_crystal_F_000             1032
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.223
_refine_diff_density_min         -0.318
_refine_diff_density_rms         0.055
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     368
_refine_ls_number_reflns         4224
_refine_ls_number_restraints     86
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.0588
_refine_ls_R_factor_gt           0.0479
_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^)+(0.0721P)^2^+0.2831P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1246
_refine_ls_wR_factor_ref         0.1362
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3417
_reflns_number_total             4224
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06095h2.cif
_cod_data_source_block           20240115_auto
_cod_original_cell_volume        2359.72(7)
_cod_database_code               1576392
_shelx_shelxl_version_number     2014/7
_chemical_oxdiff_formula         C18H12O1N2S2
_shelx_estimated_absorpt_t_max   0.806
_shelx_estimated_absorpt_t_min   0.688
_reflns_odcompleteness_completeness 99.91
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C25-N2A
 1.43 with sigma of 0.02
 C25-N2
 1.43 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C20A) \\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(S2A) \\sim Ueq, Uanis(S2)
\\sim Ueq, Uanis(C16A) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C17) \\sim Ueq,
Uanis(C17A) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C15A) \\sim Ueq, Uanis(C21A)
\\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C22A) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(S2) = Uanis(S2A)
Uanis(N2) = Uanis(N2A)
Uanis(C17) = Uanis(C17A)
Uanis(C18) = Uanis(C18A)
Uanis(C13) = Uanis(C13A)
Uanis(C14) = Uanis(C14A)
Uanis(C15) = Uanis(C15A)
Uanis(C16) = Uanis(C16A)
Uanis(C20) = Uanis(C20A)
Uanis(C19) = Uanis(C19A)
Uanis(C24) = Uanis(C24A)
Uanis(C23) = Uanis(C23A)
Uanis(C22) = Uanis(C22A)
Uanis(C21) = Uanis(C21A)
4. Others
 Sof(S2A)=Sof(N2A)=Sof(C13A)=Sof(H13A)=Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(H15A)=
 Sof(C16A)=Sof(H16A)=Sof(C17A)=Sof(C18A)=Sof(C19A)=Sof(C20A)=Sof(C21A)=
 Sof(H21A)=Sof(C22A)=Sof(H22A)=Sof(C23A)=Sof(H23A)=Sof(C24A)=Sof(H24A)=1-FVAR(1)
 Sof(S2)=Sof(N2)=Sof(C13)=Sof(H13)=Sof(C14)=Sof(H14)=Sof(C15)=Sof(H15)=
 Sof(C16)=Sof(H16)=Sof(C17)=Sof(C18)=Sof(C19)=Sof(C20)=Sof(C21)=Sof(H21)=
 Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23)=Sof(C24)=Sof(H24)=FVAR(1)
5.a Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C3(H3), C4(H4), C9(H9), C10(H10), C11(H11), C12(H12),
 C13(H13), C13A(H13A), C14(H14), C14A(H14A), C15(H15), C15A(H15A), C16(H16),
 C16A(H16A), C21(H21), C21A(H21A), C22(H22), C22A(H22A), C23(H23), C23A(H23A),
 C24(H24), C24A(H24A), C26(H26), C27(H27), C28(H28)
;
_shelx_res_checksum              56592
_shelx_hkl_checksum              92306
_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 1.431
_oxdiff_exptl_absorpt_empirical_full_min 0.821