Can time-dependent density functional theory predict intersystem crossing in organic chromophores? A case study on benzo(bis)-X-diazole based donor‒acceptor‒donor type molecules
Tam, Teck Lip Dexter; Lin, Ting Ting; Chua, Ming Hui; Phys. Chem. Chem. Phys.  (2017) –; doi:10.1039/C7CP03121A

data_7228399
_publ_section_title
;
 Can time-dependent density functional theory predict intersystem crossing
 in organic chromophores? A case study on benzo(bis)-X-diazole based
 donor--acceptor--donor type molecules
;
_journal_name_full               'Phys. Chem. Chem. Phys.'
_journal_paper_doi               10.1039/C7CP03121A
_journal_year                    2017
_chemical_formula_moiety         'C26 H32 N6 S2'
_chemical_formula_sum            'C26 H32 N6 S2'
_chemical_formula_weight         492.69
_chemical_name_systematic
;
 ?
;
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3'
_symmetry_space_group_name_Hall  '-R 3'
_symmetry_space_group_name_H-M   'R -3 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2014-02-07
_audit_creation_method
;
Olex2 1.2
(compiled 2013.12.10 svn.r2850 for OlexSys, GUI svn.r4736)
;
_audit_update_record
;
2017-03-12 deposited with the CCDC.
2017-05-25 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            9
_cell_length_a                   37.196(3)
_cell_length_b                   37.196(3)
_cell_length_c                   5.4457(9)
_cell_measurement_reflns_used    1044
_cell_measurement_temperature    250(2)
_cell_measurement_theta_max      51.352
_cell_measurement_theta_min      8.255
_cell_volume                     6524.9(13)
_computing_cell_refinement       'SAINT V7.23A (Bruker, 2005)'
_computing_data_collection       'APEX2 V2.1-4 (Bruker, 2007)'
_computing_data_reduction        'Bruker SAINT'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2008)'
_computing_structure_solution    'ShelXD (Sheldrick, 2008)'
_diffrn_ambient_temperature      250(2)
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.680
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'MX optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0326
_diffrn_reflns_av_unetI/netI     0.0372
_diffrn_reflns_Laue_measured_fraction_full 0.680
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       39
_diffrn_reflns_limit_h_min       -39
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -38
_diffrn_reflns_limit_l_max       4
_diffrn_reflns_limit_l_min       -5
_diffrn_reflns_number            4864
_diffrn_reflns_point_group_measured_fraction_full 0.680
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         55.045
_diffrn_reflns_theta_min         8.254
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    1.839
_exptl_absorpt_correction_T_max  0.7516
_exptl_absorpt_correction_T_min  0.6194
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1079 before and 0.0441 after correction.
The Ratio of minimum to maximum transmission is 0.8241.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.128
_exptl_crystal_description       needle
_exptl_crystal_F_000             2358
_exptl_crystal_size_max          0.439
_exptl_crystal_size_mid          0.035
_exptl_crystal_size_min          0.029
_refine_diff_density_max         0.126
_refine_diff_density_min         -0.092
_refine_diff_density_rms         0.024
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.013
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     201
_refine_ls_number_reflns         1791
_refine_ls_number_restraints     128
_refine_ls_restrained_S_all      1.153
_refine_ls_R_factor_all          0.0629
_refine_ls_R_factor_gt           0.0400
_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^)+(0.0684P)^2^+0.4079P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1075
_refine_ls_wR_factor_ref         0.1155
_reflns_Friedel_coverage         0.000
_reflns_number_gt                1266
_reflns_number_total             1791
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7cp03121a2.cif
_cod_data_source_block           n3239
_cod_original_cell_volume        6525.1(15)
_cod_database_code               7228399
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.949
_shelx_estimated_absorpt_t_min   0.499
_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
 S1-C5 \\sim S1-C4 \\sim S1A-C4 \\sim S1A-C6
 with sigma of 0.02
 C7-C6 \\sim C7-C4 \\sim C7A-C4 \\sim C7A-C5 \\sim C6-C5
 with sigma of 0.02
 C9-C8 \\sim C9-C10 \\sim C11A-C10 \\sim C11-C10 \\sim C12-C11 \\sim C12A-C11A
\\sim C13A-C12A \\sim C13-C12
 with sigma of 0.02
3. Rigid bond restraints
 C11A, C11, C12, C12A, C13, C13A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 S1, C7A, C7, S1A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C11A \\sim C11 \\sim C12 \\sim C12A \\sim C13 \\sim C13A: within 1.7A with
sigma of 0.04 and sigma for terminal atoms of 0.08
S1 \\sim C7A \\sim C7 \\sim S1A: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08
5. Others
 Sof(S1A)=Sof(H5B)=Sof(H6B)=Sof(C7A)=Sof(H7A)=1-FVAR(1)
 Sof(S1)=Sof(H5A)=Sof(H6A)=Sof(C7)=Sof(H7)=FVAR(1)
 Sof(H10C)=Sof(H10D)=Sof(C11)=Sof(H11A)=Sof(H11B)=Sof(C12)=Sof(H12A)=Sof(H12B)=
 Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=1-FVAR(2)
 Sof(H10A)=Sof(H10B)=Sof(C11A)=Sof(H11C)=Sof(H11D)=Sof(C12A)=Sof(H12C)=
 Sof(H12D)=Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C8(H8A,H8B), C9(H9A,H9B), C10(H10C,H10D), C10(H10A,H10B), C11(H11A,H11B),
 C12(H12A,H12B), C11A(H11C,H11D), C12A(H12C,H12D)
6.b Me refined with riding coordinates:
 C13(H13A,H13B,H13C), C13A(H13D,H13E,H13F)
6.c Aromatic/amide H refined with riding coordinates:
 C5(H5A), C5(H5B), C6(H6B), C6(H6A), C7(H7), C7A(H7A)
;
_smtbx_masks_special_details
;
The solvent masking procedure as implemented in Olex2 was used to remove the
electronic contribution of solvent molecules from the refinement.  As the exact
solvent content is not known, only the atoms used in the refinement model are
reported in the formula here.

Total solvent accessible volume / cell = 776.7 Ang^3^ [11.9%]
Total electron count / cell = 0.2
;
_shelx_res_checksum              51221