UV-irradiation of self-assembled triphenylamines affords persistent and regenerable radicals
Sindt, Ammon J.; DeHaven, Baillie A.; McEachern, David F.; Dissanayake, Madushanka M.; Smith, Mark D.; Vannucci, Aaron K.; Shimizu, Linda S.; Chemical Science  (2019) –; doi:10.1039/C8SC04607G

data_1550415
_publ_section_title
;
 UV-irradiation of self-assembled triphenylamines affords persistent and
 regenerable radicals
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/C8SC04607G
_journal_year                    2019
_chemical_formula_moiety         'C39 H32 Br2 N4 O'
_chemical_formula_sum            'C39 H32 Br2 N4 O'
_chemical_formula_weight         732.50
_space_group_crystal_system      orthorhombic
_space_group_IT_number           56
_space_group_name_Hall           '-P 2ab 2ac'
_space_group_name_H-M_alt        'P c c n'
_symmetry_space_group_name_Hall  '-P 2ab 2ac'
_symmetry_space_group_name_H-M   'P c c n'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2018-01-18
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_audit_update_record
;
2018-10-12 deposited with the CCDC.
2019-01-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.5184(8)
_cell_length_b                   19.9443(7)
_cell_length_c                   9.0043(4)
_cell_measurement_reflns_used    9851
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      26.83
_cell_measurement_theta_min      2.71
_cell_volume                     3325.6(2)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker APEX3 v2016.5-0 (Bruker, 2016)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_computing_structure_solution    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Bruker PHOTON-100 area detector'
_diffrn_detector_area_resol_mean 10.4
_diffrn_detector_type            'CMOS area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 QUEST'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0442
_diffrn_reflns_av_unetI/netI     0.0136
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       25
_diffrn_reflns_limit_k_min       -25
_diffrn_reflns_limit_l_max       11
_diffrn_reflns_limit_l_min       -11
_diffrn_reflns_number            123401
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        27.184
_diffrn_reflns_theta_max         27.184
_diffrn_reflns_theta_min         2.200
_diffrn_source                   'microfocus sealed X-ray tube'
_diffrn_source_type              'Incoatec I\ms'
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    2.475
_exptl_absorpt_correction_T_max  0.7455
_exptl_absorpt_correction_T_min  0.6811
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.0542 before and 0.0430 after correction.
The Ratio of minimum to maximum transmission is 0.9136.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.463
_exptl_crystal_description       needle
_exptl_crystal_F_000             1488
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.857
_refine_diff_density_min         -0.911
_refine_diff_density_rms         0.078
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     292
_refine_ls_number_reflns         3695
_refine_ls_number_restraints     68
_refine_ls_restrained_S_all      1.042
_refine_ls_R_factor_all          0.0561
_refine_ls_R_factor_gt           0.0440
_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^)+(0.0697P)^2^+5.2665P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1210
_refine_ls_wR_factor_ref         0.1294
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3057
_reflns_number_total             3695
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8sc04607g2.cif
_cod_data_source_block           brnph3su_dp
_cod_database_code               1550415
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.790
_shelx_estimated_absorpt_t_min   0.664
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
2. Shared sites
{O1A, O1B}
{C1A, C1B}
3. Restrained distances
 N1B-H1A = N1A-H1A
 0.84 with sigma of 0.02
 C11B-Br1B \\sim C13B-Br1B
 with sigma of 0.005
4. Restrained planarity
 N2B, C9B, C10B, C11B, C12B, Br1B, C13B, C14B
 with sigma of 0.01
5. Uiso/Uaniso restraints and constraints
Uanis(O1A) = Uanis(O1B)
Uanis(C1A) = Uanis(C1B)
Uanis(N1B) = Uanis(N1A)
Uanis(C2B) = Uanis(C2A)
Uanis(C3B) = Uanis(C3A)
Uanis(C6B) = Uanis(C7A)
Uanis(C7B) = Uanis(C6A)
Uanis(C4A) = Uanis(C8B)
Uanis(C8A) = Uanis(C5B)
Uanis(C20A) = Uanis(C16B)
Uanis(C17B) = Uanis(C19A)
Uanis(C18B) = Uanis(C18A)
Uanis(C19B) = Uanis(C17A)
Uanis(C16A) = Uanis(C20B)
Uanis(C8A) = Uanis(C4B)
Uanis(C13B) = Uanis(C14A)
Uanis(C13A) = Uanis(C12B)
Uanis(C11B) = Uanis(C12A)
Uanis(C10B) = Uanis(C11A)
Uanis(C9B) = Uanis(C10A)
Uanis(C9A) = Uanis(C14B)
Uanis(N2A) = Uanis(N2B)
6. Same fragment restrains
{Br1A, O1A, N1A, N2A, C1A, C2A, C3A, C4A, C5A, C6A, C7A, C8A, C9A, C10A, C11A,
C12A, C13A, C14A, C15A, C16A, C17A, C18A, C19A, C20A} sigma for 1-2: 0.015,
1-3: 0.04
as
{Br1B, O1B, N1B, N2B, C1B, C2B, C3B, C4B, C5B, C6B, C7B, C8B, C9B, C10B, C11B,
C12B, C13B, C14B, C15B, C16B, C17B, C18B, C19B, C20B}
7. Others
 Sof(Br1B)=Sof(N1B)=Sof(N2B)=Sof(C2B)=Sof(H2BA)=Sof(H2BB)=Sof(C3B)=Sof(C4B)=
 Sof(H4B)=Sof(C5B)=Sof(H5B)=Sof(C6B)=Sof(C7B)=Sof(H7B)=Sof(C8B)=Sof(H8B)=
 Sof(C9B)=Sof(C10B)=Sof(H10B)=Sof(C11B)=Sof(H11B)=Sof(C12B)=Sof(C13B)=Sof(H13B)=
 Sof(C14B)=Sof(H14B)=Sof(C15B)=Sof(C16B)=Sof(H16B)=Sof(C17B)=Sof(H17B)=
 Sof(C18B)=Sof(H18B)=Sof(C19B)=Sof(H19B)=Sof(C20B)=Sof(H20B)=1-FVAR(1)
 Sof(O1B)=Sof(C1B)=0.5*(1-FVAR(2))
 Sof(O1A)=Sof(C1A)=0.5*FVAR(2)
 Sof(Br1A)=Sof(N1A)=Sof(N2A)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(C3A)=Sof(C4A)=
 Sof(H4A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(C7A)=Sof(H7A)=Sof(C8A)=Sof(H8A)=
 Sof(C9A)=Sof(C10A)=Sof(H10A)=Sof(C11A)=Sof(H11A)=Sof(C12A)=Sof(C13A)=Sof(H13A)=
 Sof(C14A)=Sof(H14A)=Sof(C15A)=Sof(C16A)=Sof(H16A)=Sof(C17A)=Sof(H17A)=
 Sof(C18A)=Sof(H18A)=Sof(C19A)=Sof(H19A)=Sof(C20A)=Sof(H20A)=FVAR(1)
8.a Secondary CH2 refined with riding coordinates:
 C2A(H2AA,H2AB), C2B(H2BA,H2BB)
8.b Aromatic/amide H refined with riding coordinates:
 C4A(H4A), C5A(H5A), C7A(H7A), C8A(H8A), C10A(H10A), C11A(H11A), C13A(H13A),
 C14A(H14A), C16A(H16A), C17A(H17A), C18A(H18A), C19A(H19A), C20A(H20A),
 C4B(H4B), C5B(H5B), C7B(H7B), C8B(H8B), C10B(H10B), C11B(H11B), C13B(H13B),
 C14B(H14B), C16B(H16B), C17B(H17B), C18B(H18B), C19B(H19B), C20B(H20B)
;
_shelx_res_checksum              91937
_olex2_submission_special_instructions 'No special instructions were received'