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_1576401
_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         'C43 H26 N4 S3'
_chemical_formula_sum            'C43 H26 N4 S3'
_chemical_formula_weight         694.86
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2025-01-22
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-07-21 deposited with the CCDC.	2025-12-01 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 108.157(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   17.0229(8)
_cell_length_b                   15.4122(7)
_cell_length_c                   27.0795(11)
_cell_measurement_reflns_used    9852
_cell_measurement_temperature    298.0
_cell_measurement_theta_max      27.41
_cell_measurement_theta_min      2.393
_cell_volume                     6750.8(5)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      298.0
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.979
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1513
_diffrn_reflns_av_unetI/netI     0.0934
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       35
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            187464
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.796
_diffrn_reflns_theta_min         2.062
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.259
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6431
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0959 before and 0.0810 after correction.
The Ratio of minimum to maximum transmission is 0.8625.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.367
_exptl_crystal_description       block
_exptl_crystal_F_000             2880
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.391
_refine_diff_density_min         -0.486
_refine_diff_density_rms         0.170
_refine_ls_abs_structure_details
;
 Flack x determined using 5766 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.14(3)
_refine_ls_extinction_coef       0.0207(16)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.041
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1466
_refine_ls_number_reflns         31167
_refine_ls_number_restraints     20
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.1828
_refine_ls_R_factor_gt           0.1138
_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^)+(0.1687P)^2^+9.8364P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2890
_refine_ls_wR_factor_ref         0.3414
_reflns_Friedel_coverage         0.921
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.971
_reflns_number_gt                17407
_reflns_number_total             31167
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc06095h2.cif
_cod_data_source_block           a_a
_cod_database_code               1576401
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.975
_shelx_estimated_absorpt_t_min   0.962
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C2"-C1" \\sim C2'-C1' \\sim C2-C1 \\sim C2A-C1A
 with sigma of 0.02
3. Rigid bond restraints
 C17A, C16A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Uiso/Uaniso restraints and constraints
Uanis(C16A) \\sim Ueq, Uanis(C17A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
5.a Aromatic/amide H refined with riding coordinates:
 C6(H6), C4(H4), C10(H10), C11(H11), C8(H8), C9(H9), C16(H16), C17(H17),
 C18(H18), C19(H19), C22(H22), C23(H23), C20(H20), C21(H21), C28(H28), C29(H29),
  C30(H30), C31(H31), C35(H35), C34(H34), C33(H33), C32(H32), C40(H40),
 C41(H41), C42(H42), C43(H43), C6'(H6'), C4'(H4'), C8'(H8'), C9'(H9'),
 C10'(H10'), C11'(H11'), C16'(H16'), C17'(H17'), C18'(H18'), C19'(H19'),
 C22'(H22'), C21'(H21'), C20'(H20'), C23'(H23'), C31'(H31'), C30'(H30'),
 C29'(H29'), C28'(H28'), C35'(H35'), C34'(H34'), C33'(H33'), C32'(H32'),
 C40'(H40'), C41'(H41'), C42'(H42'), C43'(H43'), C4"(H4"), C6"(H6"), C11"(H11"),
  C10"(H10"), C9"(H9"), C8"(H8"), C19"(H19"), C18"(H18"), C17"(H17"),
 C16"(H16"), C20"(H20"), C21"(H21"), C22"(H22"), C23"(H23"), C28"(H28"),
 C29"(H29"), C30"(H30"), C31"(H31"), C33"(H33"), C34"(H34"), C35"(H35"),
 C32"(H32"), C40"(H40"), C43"(H43"), C42"(H42"), C41"(H41"), C6A(H6A), C4A(H4A),
  C10A(H10A), C11A(H11A), C8A(H8A), C9A(H9A), C19A(H19A), C18A(H18A),
 C17A(H17A), C16A(H16A), C20A(H20A), C23A(H23A), C22A(H22A), C21A(H21A),
 C31A(H31A), C30A(H30A), C29A(H29A), C28A(H28A), C32A(H32A), C33A(H33A),
 C34A(H34A), C35A(H35A), C42A(H42A), C41A(H41A), C40A(H40A), C43A(H43A)
5.b Fitted hexagon refined as free rotating group:
 C7(C6,C5,C4,C3,C2), C10(C11,C12,C13,C8,C9), C14(C15,C16,C17,C18,C19), C22(C23,
 C24,C25,C20,C21), C26(C27,C28,C29,C30,C31), C36(C35,C34,C33,C32,C37), C39(C40,
 C41,C42,C43,C38), C2'(C7',C6',C5',C4',C3'), C12'(C13',C8',C9',C10',C11'),
 C14'(C15',C16',C17',C18',C19'), C22'(C21',C20',C25',C24',C23'), C27'(C26',C31',
 C30',C29',C28'), C37'(C36',C35',C34',C33',C32'), C40'(C41',C42',C43',C38',
 C39'), C2"(C3",C4",C5",C6",C7"), C11"(C10",C9",C8",C13",C12"), C14"(C19",C18",
 C17",C16",C15"), C25"(C20",C21",C22",C23",C24"), C26"(C27",C28",C29",C30",
 C31"), C33"(C34",C35",C36",C37",C32"), C40"(C39",C38",C43",C42",C41"), C2A(C7A,
 C6A,C5A,C4A,C3A), C10A(C11A,C12A,C13A,C8A,C9A), C15A(C14A,C19A,C18A,C17A,C16A),
  C20A(C25A,C24A,C23A,C22A,C21A), C26A(C31A,C30A,C29A,C28A,C27A), C37A(C32A,
 C33A,C34A,C35A,C36A), C42A(C41A,C40A,C39A,C38A,C43A)
;
_shelx_res_checksum              65390
_shelx_hkl_checksum              68859
_olex2_submission_special_instructions 'No special instructions were received'