Photophysical and redox properties of new donor-acceptor-donor (DAD) compounds containing benzothiadiazole (A) and dimethyldihydroacridine (D) units: a combined experimental and theoretical study.
Polesiak, Emilia; Makowska-Janusik, Malgorzata; Drapala, Jakub; Zagorska, Malgorzata; Banasiewicz, Marzena; Kozankiewicz, Boleslaw; Kulszewicz-Bajer, Irena; Pron, Adam; Physical chemistry chemical physics : PCCP 26 (2024) 20690–20700; doi:10.1039/d4cp02322f

data_7249042
_publ_section_title
;
 Photophysical and redox properties of new donor-acceptor-donor (DAD)
 compounds containing benzothiadiazole (A) and dimethyldihydroacridine (D)
 units: a combined experimental and theoretical study.
;
_journal_issue                   30
_journal_name_full               'Physical chemistry chemical physics : PCCP'
_journal_page_first              20690
_journal_page_last               20700
_journal_paper_doi               10.1039/d4cp02322f
_journal_volume                  26
_journal_year                    2024
_chemical_formula_moiety         'C48 H38 N4 S, 2(C4 H8 O)'
_chemical_formula_sum            'C56 H54 N4 O2 S'
_chemical_formula_weight         847.09
_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_creation_date             2024-05-09
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-06-03 deposited with the CCDC.	2024-07-11 downloaded from the CCDC.
;
_cell_angle_alpha                96.230(2)
_cell_angle_beta                 91.199(2)
_cell_angle_gamma                114.121(2)
_cell_formula_units_Z            2
_cell_length_a                   12.2872(3)
_cell_length_b                   12.8272(3)
_cell_length_c                   15.3688(3)
_cell_measurement_reflns_used    30772
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      70.1620
_cell_measurement_theta_min      3.9430
_cell_volume                     2192.03(9)
_computing_cell_refinement       'CrysAlisPro 1.171.41.76a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.76a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.76a (Rigaku OD, 2020)'
_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    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 16.2974
_diffrn_detector_type            Eos
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.996
_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    -69.00  21.00   1.00    1.00    --    0.00 -57.00 -30.00   90
  2  \w    -11.00  36.00   1.00    1.00    --    0.00 -88.00-179.00   47
  3  \w    -21.00  69.00   1.00    1.00    --    0.00  57.00 120.00   90
  4  \w    -15.00  75.00   1.00    2.50    --   54.00 -57.00 -30.00   90
  5  \w    -18.00  80.00   1.00    2.50    --   54.00 -37.00  60.00   98
  6  \w    -15.00  75.00   1.00    2.50    --   54.00 -57.00  90.00   90
  7  \w     10.00 127.00   1.00    2.50    --   54.00  19.00 -90.00  117
  8  \w    -18.00  80.00   1.00    2.50    --   54.00 -37.00 -90.00   98
  9  \w      1.00  96.00   1.00    2.50    --   54.00 -99.00-120.00   95
 10  \w     23.00 111.00   1.00    2.50    --   54.00-125.00 150.00   88
 11  \w     35.00 142.00   1.00    5.00    --  108.00 -25.00-120.00  107
 12  \w     36.00 113.00   1.00    5.00    --  108.00-111.00  30.00   77
 13  \w     36.00 113.00   1.00    5.00    --  108.00-111.00 -90.00   77
 14  \w     36.00 134.00   1.00    5.00    --  108.00 -37.00 120.00   98
 15  \w     74.00 178.00   1.00    5.00    --  108.00  25.00  90.00  104
 16  \w    100.00 178.00   1.00    5.00    --  108.00 111.00  60.00   78
 17  \w     36.00 113.00   1.00    5.00    --  108.00-111.00 120.00   77
 18  \w     57.00 150.00   1.00    5.00    --  108.00 178.00 -60.00   93
 19  \w     86.00 178.00   1.00    5.00    --  108.00  50.00-120.00   92
 20  \w     36.00 178.00   1.00    5.00    --  108.00  12.00 150.00  142
 21  \w     38.00 138.00   1.00    5.00    --  108.00 -77.00 -30.00  100
 22  \w     36.00 113.00   1.00    5.00    --  108.00-111.00-180.00   77
 23  \w     36.00 146.00   1.00    5.00    --  108.00 -91.00 -90.00  110
 24  \w     36.00 146.00   1.00    5.00    --  108.00 -91.00  60.00  110
 25  \w     86.00 178.00   1.00    5.00    --  108.00  50.00 -30.00   92
 26  \w     40.00 130.00   1.00    5.00    --  108.00 -63.00 120.00   90
 27  \w     74.00 178.00   1.00    5.00    --  108.00  25.00-150.00  104
 28  \w     36.00 113.00   1.00    5.00    --  108.00-111.00 -60.00   77
 29  \w     83.00 178.00   1.00    5.00    --  108.00  39.00-128.32   95
 30  \w     86.00 176.00   1.00    5.00    --  108.00  63.00 -90.00   90
 31  \w     36.00 113.00   1.00    5.00    --  108.00-111.00-150.00   77
 32  \w     36.00 146.00   1.00    5.00    --  108.00 -91.00   0.00  110
 33  \w     38.00 130.00   1.00    5.00    --  108.00 -50.00   0.00   92
 34  \w     40.00 130.00   1.00    5.00    --  108.00 -63.00 150.00   90
 35  \w     36.00 178.00   1.00    5.00    --  108.00  12.00  60.00  142
 36  \w     36.00 178.00   1.00    5.00    --  108.00  12.00-180.00  142
 37  \w     57.00 150.00   1.00    5.00    --  108.00 178.00  60.00   93
 38  \w     36.00 113.00   1.00    5.00    --  108.00-111.00 150.00   77
 39  \w     86.00 176.00   1.00    5.00    --  108.00  63.00-150.00   90
 40  \w     57.00 150.00   1.00    5.00    --  108.00 178.00   0.00   93
 41  \w     38.00 138.00   1.00    5.00    --  108.00 -77.00   0.00  100
 42  \w    101.00 127.00   1.00    5.00    --  108.00 -91.00 -60.00   26
 43  \w    129.00 155.00   1.00    5.00    --  108.00  12.00  90.00   26
 44  \w     52.00  78.00   1.00    5.00    --  108.00 -50.00 -30.00   26
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Eos'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1257157000
_diffrn_orient_matrix_UB_12      -0.0655111000
_diffrn_orient_matrix_UB_13      -0.0469302000
_diffrn_orient_matrix_UB_21      0.0413991000
_diffrn_orient_matrix_UB_22      0.0688216000
_diffrn_orient_matrix_UB_23      -0.0782500000
_diffrn_orient_matrix_UB_31      0.0381005000
_diffrn_orient_matrix_UB_32      -0.0926170000
_diffrn_orient_matrix_UB_33      -0.0435333000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0216
_diffrn_reflns_av_unetI/netI     0.0168
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.996
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       18
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            41253
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.996
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.064
_diffrn_reflns_theta_min         2.900
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.035
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.558
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.76a (Rigaku Oxford Diffraction, 2020)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear yellow'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.283
_exptl_crystal_description       needle
_exptl_crystal_F_000             900
_exptl_crystal_recrystallization_method 'Re-crystallisation from solvent: THF'
_exptl_crystal_size_max          0.716
_exptl_crystal_size_mid          0.185
_exptl_crystal_size_min          0.101
_refine_diff_density_max         0.841
_refine_diff_density_min         -0.646
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.021
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     595
_refine_ls_number_reflns         8288
_refine_ls_number_restraints     37
_refine_ls_restrained_S_all      1.023
_refine_ls_R_factor_all          0.0423
_refine_ls_R_factor_gt           0.0409
_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^)+(0.0609P)^2^+1.1522P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1092
_refine_ls_wR_factor_ref         0.1098
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8071
_reflns_number_total             8288
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cp02322f2.cif
_cod_data_source_block           ikb890_01
_cod_depositor_comments          'Adding full bibliography for 7249042.cif.'
_cod_database_code               7249042
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C20 H20 N4 S1'
_shelx_estimated_absorpt_t_max   0.903
_shelx_estimated_absorpt_t_min   0.525
_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
 O1-C52 \\sim O1-C52A
 with sigma of 0.02
 C50-C51 \\sim C50-C51A
 with sigma of 0.02
 C51-H51a \\sim C51A-H51c
 with sigma of 0.02
 C51-H51b \\sim C51A-H51d
 with sigma of 0.02
 C51-C52 \\sim C51A-C52A
 with sigma of 0.02
 C52-H52a \\sim C52A-H52c
 with sigma of 0.02
 C52-H52b \\sim C52A-H52d
 with sigma of 0.02
 O1-C51 \\sim O1-C51A
 with sigma of 0.04
 O1-H52a \\sim O1-H52c
 with sigma of 0.04
 O1-H52b \\sim O1-H52d
 with sigma of 0.04
 C50-H51a \\sim C50-H51c
 with sigma of 0.04
 C50-H51b \\sim C50-H51d
 with sigma of 0.04
 C50-C52 \\sim C50-C52A
 with sigma of 0.04
 C51-H52a \\sim C51A-H52c
 with sigma of 0.04
 C51-H52b \\sim C51A-H52d
 with sigma of 0.04
 H51a-H51b \\sim H51c-H51d
 with sigma of 0.04
 H51a-C52 \\sim H51c-C52A
 with sigma of 0.04
 H51b-C52 \\sim H51d-C52A
 with sigma of 0.04
 H52a-H52b \\sim H52c-H52d
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(O2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.01
Uanis(C51A) \\sim Ueq, Uanis(C52A) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.01
4. Others
 Sof(H50c)=Sof(H50d)=Sof(C52A)=Sof(H52c)=Sof(H52d)=Sof(C51A)=Sof(H51c)=
 Sof(H51d)=1-FVAR(1)
 Sof(H50a)=Sof(H50b)=Sof(C51)=Sof(H51a)=Sof(H51b)=Sof(C52)=Sof(H52a)=Sof(H52b)=
 FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C49(H49a,H49b), C50(H50a,H50b), C50(H50c,H50d), C51(H51a,H51b), C52(H52a,
 H52b), C53(H53a,H53b), C54(H54a,H54b), C55(H55a,H55b), C56(H56a,H56b),
 C52A(H52c,H52d), C51A(H51c,H51d)
5.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C8(H8), C9(H9), C11(H11), C12(H12), C14(H14), C15(H15),
 C17(H17), C18(H18), C20(H20), C21(H21), C22(H22), C23(H23), C29(H29), C30(H30),
  C31(H31), C32(H32), C35(H35), C36(H36), C37(H37), C38(H38), C44(H44),
 C45(H45), C46(H46), C47(H47)
5.c Idealised Me refined as rotating group:
 C26(H26a,H26b,H26c), C27(H27a,H27b,H27c), C41(H41a,H41b,H41c), C42(H42a,H42b,
 H42c)
;
_shelx_res_checksum              3394
_olex2_date_sample_data_collection 2024-04-19
_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 1.992
_oxdiff_exptl_absorpt_empirical_full_min 0.740