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_7228401
_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
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2013-12-12
_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                80.5235(16)
_cell_angle_beta                 89.0924(16)
_cell_angle_gamma                79.1833(15)
_cell_formula_units_Z            4
_cell_length_a                   9.6442(3)
_cell_length_b                   13.9072(4)
_cell_length_c                   19.3218(6)
_cell_measurement_reflns_used    9679
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      34.951
_cell_measurement_theta_min      2.406
_cell_volume                     2510.43(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    'XM (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.07
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.998
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0729
_diffrn_reflns_av_unetI/netI     0.0335
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -31
_diffrn_reflns_number            189236
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         35.015
_diffrn_reflns_theta_min         1.069
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    0.239
_exptl_absorpt_correction_T_max  0.7164
_exptl_absorpt_correction_T_min  0.6791
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.1109 before and 0.0939 after correction.
The Ratio of minimum to maximum transmission is 0.9479.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.304
_exptl_crystal_description       block
_exptl_crystal_F_000             1048
_exptl_crystal_size_max          0.558
_exptl_crystal_size_mid          0.347
_exptl_crystal_size_min          0.232
_refine_diff_density_max         1.592
_refine_diff_density_min         -1.475
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.026
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     609
_refine_ls_number_reflns         22113
_refine_ls_number_restraints     312
_refine_ls_restrained_S_all      1.394
_refine_ls_R_factor_all          0.0570
_refine_ls_R_factor_gt           0.0499
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0503P)^2^+1.9032P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1226
_refine_ls_wR_factor_ref         0.1292
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19515
_reflns_number_total             22113
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c7cp03121a2.cif
_cod_data_source_block           n3230
_cod_database_code               7228401
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.947
_shelx_estimated_absorpt_t_min   0.878
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 S1-C7 \\sim S1-C10 \\sim S2-C14 \\sim S2-C11 \\sim S4-C40 \\sim S4-C37 \\sim
S3-C33 \\sim S3-C36 \\sim S1A-C7
 \\sim S1A-C9 \\sim S2A-C11 \\sim S2A-C13 \\sim S4A-C39 \\sim S4A-C37 \\sim
S3A-C33 \\sim S3A-C35
 with sigma of 0.02
 C8-C7 \\sim C9-C8 \\sim C9-C10 \\sim C12-C11 \\sim C13-C12 \\sim C14-C13 \\sim
C38-C37 \\sim C39-C38 -
 C40-C39 \\sim C34-C33 \\sim C35-C34 \\sim C36-C35 \\sim C9-C10 \\sim C8A-C10
\\sim C8A-C7 \\sim C12A-C11 -
 C14-C12A \\sim C14-C13 \\sim C36-C35 \\sim C34A-C33 \\sim C40-C39 \\sim
C40-C38A \\sim C37-C38A \\sim C34A-
 C36
 with sigma of 0.01
 C36-C35 \\sim C36-C34A \\sim C34A-C33 \\sim C38A-C37 \\sim C40-C38A \\sim
C40-C39 \\sim C12A-C11 -
 C14-C12A \\sim C14-C13 \\sim C9-C10 \\sim C8A-C10 \\sim C8A-C7
 with sigma of 0.01
3. Restrained planarity
 C33, C34A, C36, C35, S3A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(S2) = Uanis(S3) = Uanis(S4) = Uanis(S1) = Uanis(S1A) = Uanis(S2A) =
Uanis(S3A) = Uanis(S4A)
Uanis(C34A) = Uanis(C8A) = Uanis(C12A) = Uanis(C38A) = Uanis(C34) = Uanis(C8) =
Uanis(C12) = Uanis(C38)
5. Others
 Sof(S1A)=Sof(C8A)=Sof(H8A)=Sof(H9B)=Sof(H10A)=1-FVAR(1)
 Sof(S1)=Sof(C8)=Sof(H8)=Sof(H9)=Sof(H10)=FVAR(1)
 Sof(S2A)=Sof(C12A)=Sof(H12A)=Sof(H13A)=Sof(H14A)=1-FVAR(2)
 Sof(S2)=Sof(C12)=Sof(H12)=Sof(H13)=Sof(H14)=FVAR(2)
 Sof(S3A)=Sof(C34A)=Sof(H34A)=Sof(H35A)=Sof(H36A)=1-FVAR(3)
 Sof(S3)=Sof(C34)=Sof(H34)=Sof(H35)=Sof(H36)=FVAR(3)
 Sof(S4A)=Sof(C38A)=Sof(H38A)=Sof(H39A)=Sof(H40A)=1-FVAR(4)
 Sof(S4)=Sof(C38)=Sof(H38)=Sof(H39)=Sof(H40)=FVAR(4)
6.a Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,
 H19B), C21(H21A,H21B), C22(H22A,H22B), C23(H23A,H23B), C24(H24A,H24B),
 C25(H25A,H25B), C41(H41A,H41B), C42(H42A,H42B), C43(H43A,H43B), C44(H44A,H44B),
  C45(H45A,H45B), C47(H47A,H47B), C48(H48A,H48B), C49(H49A,H49B), C50(H50A,
 H50B), C51(H51A,H51B)
6.b Aromatic/amide H refined with riding coordinates:
 C8(H8), C8A(H8A), C9(H9), C9(H9B), C10(H10), C10(H10A), C12(H12), C12A(H12A),
 C13(H13), C13(H13A), C14(H14), C14(H14A), C34(H34), C34A(H34A), C35(H35),
 C35(H35A), C36(H36), C36(H36A), C38(H38), C38A(H38A), C39(H39), C39(H39A),
 C40(H40), C40(H40A)
6.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C26(H26A,H26B,H26C), C46(H46A,H46B,H46C), C52(H52A,H52B,
 H52C)
;
_shelx_res_checksum              12581