One- and Two-Electron Reduction of Triarylborane-Based Helical Donor-Acceptor Compounds
Jia, Xiangqing; Nitsch, Jörn; Wu, Zhu; Friedrich, Alexandra; Krebs, Johannes; Krummenacher, Ivo; Fantuzzi, Felipe; Braunschweig, Holger; Moos, Michael; Lambert, Christoph; Engels, Bernd; Marder, Todd B.; Chemical Science  (2021) –; doi:10.1039/D1SC02409D

data_1564258
_publ_section_title
;
 One- and Two-Electron Reduction of Triarylborane-Based Helical
 Donor-Acceptor Compounds
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D1SC02409D
_journal_year                    2021
_chemical_formula_moiety         'C50 H46 B N, C12 H24 K O6, 3(C4 H8 O)'
_chemical_formula_sum            'C74 H94 B K N O9'
_chemical_formula_weight         1191.41
_chemical_name_systematic
'10-(dimesitylboryl)-N,N-di-p-tolylbenzo[c]phenanthren-4-amine (3-B(Mes)2-[4]helix-9-N(p-Tol)2) monoanion'
_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             2019-09-30
_audit_creation_method
;
Olex2 1.2-ac3
(compiled 2017.03.02 svn.r3394 for Rigaku Oxford Diffraction, GUI svn.r5318)
;
_audit_update_record
;
2020-11-13 deposited with the CCDC.	2021-07-27 downloaded from the CCDC.
;
_cell_angle_alpha                98.375(2)
_cell_angle_beta                 90.741(2)
_cell_angle_gamma                103.958(2)
_cell_formula_units_Z            2
_cell_length_a                   12.5786(3)
_cell_length_b                   16.3020(4)
_cell_length_c                   16.8804(3)
_cell_measurement_reflns_used    24252
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      70.0680
_cell_measurement_theta_min      2.6500
_cell_volume                     3319.24(13)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_molecular_graphics    'ShelXLe (Huebschle et all, 2011)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL-2018/3 (Sheldrick, 2018)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.992
_diffrn_measured_fraction_theta_max 0.988
_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    -20.00  57.00   0.50    7.00    --   50.30 -52.00  -9.00  154
  2  \w      4.00  47.00   0.50    7.00    --   50.30   0.00 -30.00   86
  3  \w     97.00 123.00   0.50   27.00    --  105.75  61.00  60.00   52
  4  \w    132.00 170.00   0.50   27.00    --  105.75  61.00  60.00   76
  5  \w    136.00 178.00   0.50   27.00    --  105.75  52.00 136.00   84
  6  \w    114.00 173.00   0.50   27.00    --  105.75  15.00  60.00  118
  7  \w     96.00 123.00   0.50   27.00    --  105.75  52.00 136.00   54
  8  \w     74.00 104.00   0.50   27.00    --  105.75   0.00  90.00   60
  9  \w     46.00 105.00   0.50    7.00    --   50.30  52.00 136.00  118
 10  \w     34.00  70.00   0.50   27.00    --  105.75 -61.00   0.00   72
 11  \w     36.00 108.00   0.50   27.00    --  105.75-109.00  14.08  144
 12  \w     50.00 116.00   0.50   27.00    --  105.75-131.00  95.07  132
 13  \w     47.00 122.00   0.50   27.00    --  105.75-140.00  -8.93  150
 14  \w     83.00 108.00   0.50   27.00    --  105.75-111.00-123.03   50
 15  \w     40.00 111.00   0.50   27.00    --  105.75-125.00-120.00  142
 16  \w     44.00  85.00   0.50   27.00    --  105.75 -94.00 -90.00   82
 17  \w     35.00 111.00   0.50   27.00    --  105.75-125.00   0.00  152
 18  \w     45.00  71.00   0.50   27.00    --  105.75 -61.00 120.00   52
 19  \w     40.00 106.00   0.50   27.00    --  105.75 -77.00  90.00  132
 20  \w     38.00 108.00   0.50   27.00    --  105.75-107.00 103.59  140
 21  \w     68.00 107.00   0.50   27.00    --  105.75   0.00 -60.00   78
 22  \w    105.00 177.00   0.50   27.00    --  105.75  30.00 -90.00  144
 23  \w     57.00  93.00   0.50   27.00    --  105.75   0.00 -90.00   72
 24  \w     58.00 112.00   0.50   27.00    --  105.75   0.00-150.00  108
 25  \w     39.00  71.00   0.50   27.00    --  105.75-111.00-123.03   64
 26  \w     40.00 109.00   0.50   27.00    --  105.75-114.00 -98.45  138
 27  \w     35.00 110.00   0.50   27.00    --  105.75-125.00-150.00  150
 28  \w     16.00  57.00   0.50    7.00    --   50.30   0.00-180.00   82
 29  \w    -23.00  20.00   0.50    7.00    --  -50.24  19.00-120.00   86
 30  \w    -68.00 -13.00   0.50   27.00    --  -84.25  61.00 -60.00  110
 31  \w   -118.00 -54.00   0.50    7.00    --  -50.24 -52.00  -9.00  128
 32  \w    -52.00  15.00   0.50    7.00    --  -50.24  52.00 136.00  134
 33  \w    -49.00 -12.00   0.50   27.00    --  -84.25  52.00 136.00   74
 34  \w   -121.00 -85.00   0.50    7.00    --  -50.24-125.00 -60.00   72
 35  \w   -150.00 -75.00   0.50   27.00    --  -84.25 -52.00  -9.00  150
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0183541000
_diffrn_orient_matrix_UB_12      -0.0828862000
_diffrn_orient_matrix_UB_13      -0.0608530000
_diffrn_orient_matrix_UB_21      0.1126616000
_diffrn_orient_matrix_UB_22      -0.0113889000
_diffrn_orient_matrix_UB_23      0.0262247000
_diffrn_orient_matrix_UB_31      -0.0541958000
_diffrn_orient_matrix_UB_32      -0.0520631000
_diffrn_orient_matrix_UB_33      0.0643430000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0583
_diffrn_reflns_av_unetI/netI     0.0339
_diffrn_reflns_Laue_measured_fraction_full 0.992
_diffrn_reflns_Laue_measured_fraction_max 0.988
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -19
_diffrn_reflns_number            42082
_diffrn_reflns_point_group_measured_fraction_full 0.992
_diffrn_reflns_point_group_measured_fraction_max 0.988
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         70.058
_diffrn_reflns_theta_min         2.649
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.149
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68341
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019) Empirical 
absorption correction using spherical harmonics, implemented in SCALE3 
ABSPACK scaling algorithm.
;
_exptl_crystal_colour            black
_exptl_crystal_density_diffrn    1.192
_exptl_crystal_description       block
_exptl_crystal_F_000             1282
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: Tetrahydrofuran'
_exptl_crystal_size_max          0.245
_exptl_crystal_size_mid          0.184
_exptl_crystal_size_min          0.056
_refine_diff_density_max         0.741
_refine_diff_density_min         -0.460
_refine_diff_density_rms         0.053
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     935
_refine_ls_number_reflns         12455
_refine_ls_number_restraints     586
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0680
_refine_ls_R_factor_gt           0.0601
_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^)+(0.1050P)^2^+1.2153P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1716
_refine_ls_wR_factor_ref         0.1818
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10489
_reflns_number_total             12455
_reflns_threshold_expression     'I > 2\s(I)'
_twin_special_details
;
Component 2 rotated by 17.5012\% 
 around [-0.77 -0.50 0.40] (reciprocal) or [-0.89 -0.44 0.15] (direct)
;
_cod_data_source_file            d1sc02409d2.cif
_cod_data_source_block           cmpd_1K1
_cod_database_code               1564258
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_usercomment     jxq2-27
_shelx_estimated_absorpt_t_max   0.938
_shelx_estimated_absorpt_t_min   0.766
_diffrn_oxdiff_digest_frames
;
019ff81479cd11082f70f10a9a0a2d755103640fffd
;
_diffrn_oxdiff_digest_hkl
;
014178addd1f89adc334aefbc36ee7820fde05
;
_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
 C9B_1-C10B_1 = C7B_1-C8B_1 = C9A_1-C10A_1 = C7A_1-C8A_1 = C8A_1-C9A_1 = C8B_1-
 C9B_1
 1.52 with sigma of 0.01
 O4A_1-C7A_1 = O4A_1-C10A_1 = O4B_1-C7B_1 = O4B_1-C10B_1
 1.43 with sigma of 0.01
 O4A_1-C8A_1 = O4A_1-C9A_1 = O4B_1-C8B_1 = O4B_1-C9B_1
 2.37 with sigma of 0.01
 C7A_1-C10A_1 = C7B_1-C10B_1
 2.33 with sigma of 0.01
 C8A_1-C10A_1 = C7A_1-C9A_1 = C7B_1-C9B_1 = C8B_1-C10B_1
 2.36 with sigma of 0.01
 C1A_3-C2A_3 = C2A_3-C3A_3 = C3A_3-C4A_3
 1.52 with sigma of 0.01
 C3A_3-O1A_3 = O1A_3-C2A_3
 2.37 with sigma of 0.01
 C1A_3-C3A_3 = C2A_3-C4A_3
 2.36 with sigma of 0.01
 C1A_3-O1A_3 = O1A_3-C4A_3
 1.43 with sigma of 0.01
 C1A_3-C4A_3
 2.33 with sigma of 0.01
 C3B_3-C5B_3 = C4B_3-C1B_3
 2.36 with sigma of 0.01
 O2B_3-C4B_3 = O2B_3-C5B_3
 2.37 with sigma of 0.01
 C1B_3-O2B_3 = O2B_3-C3B_3
 1.43 with sigma of 0.01
 C3B_3-C4B_3 = C4B_3-C5B_3 = C5B_3-C1B_3
 1.52 with sigma of 0.01
 C1B_3-C3B_3
 2.33 with sigma of 0.01
 O1C_3-C2C_3 = C5C_3-O1C_3
 1.43 with sigma of 0.01
 C2C_3-C3C_3 = C3C_3-C4C_3 = C4C_3-C5C_3
 1.52 with sigma of 0.01
 O1C_3-C3C_3 = C4C_3-O1C_3
 2.37 with sigma of 0.01
 C2C_3-C4C_3 = C3C_3-C5C_3 = C2C_3-C5C_3
 2.36 with sigma of 0.01
 C2C_3-C5C_3
 2.33 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O4A_1 \\sim C7A_1 \\sim C8A_1 \\sim C9A_1 \\sim C10A_1 \\sim O4B_1 \\sim C8B_1
\\sim C7B_1 \\sim C9B_1 \\sim C10B_1: within 2A with sigma of 0.003 and sigma
for terminal atoms of 0.006
C9A_2 \\sim C9B_2: within 2A with sigma of 0.003 and sigma for terminal atoms
of 0.006
C1A_3 \\sim C2A_3 \\sim O1A_3 \\sim C4A_3 \\sim C3A_3 \\sim C5B_3 \\sim C1B_3
\\sim O2B_3 \\sim C3B_3 \\sim C4B_3 \\sim C4C_3 \\sim O1C_3 \\sim C2C_3 \\sim
C3C_3 \\sim C5C_3: within 2A with sigma of 0.008 and sigma for terminal atoms
of 0.016
4. Others
 1*[Sof(C1A)+Sof(H1AA)+Sof(H1AB)+Sof(C2A)+Sof(H2AA)+Sof(H2AB)+Sof(O1A)+
 Sof(C4A)+Sof(H4A1)+Sof(H4A2)+Sof(C3A)+Sof(H3A1)+Sof(H3A2)]+1*[Sof(C5B)+
 Sof(H5B1)+Sof(H5B2)+Sof(C1B)+Sof(H1BA)+Sof(H1BB)+Sof(O2B)+Sof(C3B)+Sof(H3BA)+
 Sof(H3BB)+Sof(C4B)+Sof(H4B1)+Sof(H4B2)]+1*[Sof(C4C)+Sof(H4CA)+Sof(H4CB)+
 Sof(O1C)+Sof(C2C)+Sof(H2CA)+Sof(H2CB)+Sof(C3C)+Sof(H3CA)+Sof(H3CB)+Sof(C5C)+
 Sof(H5CA)+Sof(H5CB)]=1 with esd of 0.0001
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=Sof(O1A)=Sof(C4A)=
 Sof(H4A1)=Sof(H4A2)=Sof(C3A)=Sof(H3A1)=Sof(H3A2)=FVAR(1)
 Sof(C5B)=Sof(H5B1)=Sof(H5B2)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(O2B)=Sof(C3B)=
 Sof(H3BA)=Sof(H3BB)=Sof(C4B)=Sof(H4B1)=Sof(H4B2)=FVAR(2)
 Sof(C4C)=Sof(H4CA)=Sof(H4CB)=Sof(O1C)=Sof(C2C)=Sof(H2CA)=Sof(H2CB)=Sof(C3C)=
 Sof(H3CA)=Sof(H3CB)=Sof(C5C)=Sof(H5CA)=Sof(H5CB)=FVAR(3)
 Sof(C9B)=Sof(H9BA)=Sof(H9BB)=1-FVAR(4)
 Sof(C9A)=Sof(H9AA)=Sof(H9AB)=FVAR(4)
 Sof(O4B)=Sof(C8B)=Sof(H8BA)=Sof(H8BB)=Sof(C7B)=Sof(H7BA)=Sof(H7BB)=Sof(C9B)=
 Sof(H9BA)=Sof(H9BB)=Sof(C10B)=Sof(H10C)=Sof(H10D)=1-FVAR(5)
 Sof(O4A)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(C9A)=
 Sof(H9AA)=Sof(H9AB)=Sof(C10A)=Sof(H10A)=Sof(H10B)=FVAR(5)
5.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1AB), C2(H2A,H2AB), C3(H3A,H3AB), C7A(H7AA,H7AB), C8A(H8AA,H8AB),
 C9A(H9AA,H9AB), C10A(H10A,H10B), C8B(H8BA,H8BB), C7B(H7BA,H7BB), C9B(H9BA,
 H9BB), C10B(H10C,H10D), C5(H5A,H5AB), C6(H6A,H6AB), C4(H4A,H4AB), C1(H1A,H1AB),
  C2(H2A,H2AB), C3(H3A,H3AB), C5(H5A,H5AB), C6(H6A,H6AB), C7(H7A,H7AB),
 C9A(H9AA,H9AB), C9B(H9BA,H9BB), C4(H4A,H4AB), C1A(H1AA,H1AB), C2A(H2AA,H2AB),
 C4A(H4A1,H4A2), C3A(H3A1,H3A2), C5B(H5B1,H5B2), C1B(H1BA,H1BB), C3B(H3BA,H3BB),
  C4B(H4B1,H4B2), C4C(H4CA,H4CB), C2C(H2CA,H2CB), C3C(H3CA,H3CB), C5C(H5CA,H5CB)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C9(H9), C10(H10), C24(H24), C12(H12),
 C13(H13), C16(H16), C17(H17), C18(H18), C22(H22), C21(H21), C25(H25), C27(H27),
  C29(H29), C30(H30), C37(H37), C35(H35), C46(H46), C44(H44)
5.c Idealised Me refined as rotating group:
 C7(H7A,H7B,H7C), C14(H14A,H14B,H14C), C39(H39A,H39B,H39C), C50(H50A,H50B,
 H50C), C49(H49A,H49B,H49C), C48(H48A,H48B,H48C), C41(H41A,H41B,H41C), C40(H40A,
 H40B,H40C)
;
_shelx_res_checksum              42930
_shelx_hkl_checksum              34496
_olex2_date_sample_data_collection 2019-08-06
_olex2_date_sample_submission    2019-08-05
_olex2_exptl_crystal_mounting_method
;
The crystal was immersed in a film of perfluoropolyether oil, mounted on a 
 polyimide microloop (MicroMounts of MiTeGen) and transferred to stream of cold 
 nitrogen (Oxford Cryostream 800).'
;
_olex2_submission_original_sample_id jxq2-27
_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 1.424
_oxdiff_exptl_absorpt_empirical_full_min 0.696
_oxdiff_twin_integration_method  simultaneous
_oxdiff_twin_items               2