Functionalized cationic [4]helicenes with unique tuning of absorption, fluorescence and chiroptical properties up to the far-red range
Delgado, I. Hernández; Pascal, S.; Wallabregue, A.; Duwald, R.; Besnard, C.; Guénée, L.; Nançoz, C.; Vauthey, E.; Tovar, R. C.; Lunkley, J. L.; Muller, G.; Lacour, J.; Chem. Sci. 7 (2016) 4685–; doi:10.1039/C6SC00614K

data_1543071
_publ_section_title
;
 Functionalized cationic [4]helicenes with unique tuning of absorption,
 fluorescence and chiroptical properties up to the far-red range
;
_journal_issue                   7
_journal_name_full               'Chem. Sci.'
_journal_page_first              4685
_journal_paper_doi               10.1039/C6SC00614K
_journal_volume                  7
_journal_year                    2016
_chemical_formula_moiety         'C31 H36 N3 O3, B F4'
_chemical_formula_sum            'C31 H36 B F4 N3 O3'
_chemical_formula_weight         585.44
_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     direct
_audit_creation_date             2015-04-08
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3150 for OlexSys, GUI svn.r4998)
;
_audit_update_record
;
2015-12-21 deposited with the CCDC.
2016-04-08 downloaded from the CCDC.
;
_cell_angle_alpha                108.555(3)
_cell_angle_beta                 106.512(3)
_cell_angle_gamma                97.631(3)
_cell_formula_units_Z            2
_cell_length_a                   8.8012(3)
_cell_length_b                   13.0835(4)
_cell_length_c                   14.2973(4)
_cell_measurement_reflns_used    11183
_cell_measurement_temperature    179.95(10)
_cell_measurement_theta_max      73.3500
_cell_measurement_theta_min      3.6420
_cell_volume                     1450.56(9)
_computing_cell_refinement
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_collection
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_computing_data_reduction
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
;
_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    'SIR2004 (Burla et al., 2007)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      179.95(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4679
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_details
;
  1 omega -108.00  -12.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865  -37.0000    0.0000 96

  2 omega  -29.00   30.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865   37.0000 -150.0000 59

  3 omega  -34.00   36.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865   37.0000  -30.0000 70

  4 omega -112.00  -42.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865 -178.0000   30.0000 70

  5 omega -123.00  -37.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865  178.0000  150.0000 86

  6 omega   88.00  125.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       37.6865  178.0000  120.0000 37

  7 omega   62.00  113.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999 -111.0000  150.0000 51

  8 omega   91.00  175.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   30.0000 -180.0000 84

  9 omega   38.00   94.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  -45.0000  120.0000 56

 10 omega   29.00   57.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  -30.0000    0.0000 28

 11 omega  149.00  175.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  111.0000  -60.0000 26

 12 omega   27.00  104.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  -94.0000 -120.0000 77

 13 omega   34.00  106.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  -94.0000  -60.0000 72

 14 omega   44.00   86.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  -45.0000  -90.0000 42

 15 omega   75.00  105.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   30.0000   30.0000 30

 16 omega   42.00   93.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  -45.0000   30.0000 51

 17 omega  140.00  168.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   30.0000   30.0000 28

 18 omega  102.00  154.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  111.0000  -90.0000 52

 19 omega  107.00  147.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  111.0000   30.0000 40

 20 omega   81.00  177.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   45.0000   90.0000 96

 21 omega   33.00  105.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  -94.0000   30.0000 72

 22 omega   61.00   86.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  -83.0000  106.0000 25

 23 omega  -92.00  -66.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865  -57.0000   90.0000 26

 24 omega  -50.00   -7.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865  -57.0000   90.0000 43

 25 omega  -41.00  -16.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865  -37.0000 -120.0000 25

 26 omega -115.00  -49.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865  -57.0000 -150.0000 66

 27 omega  -47.00  -11.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865  -57.0000 -150.0000 36

 28 omega   -5.00   20.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       37.6865   96.0000  -97.1471 25

 29 omega   10.00   35.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       48.0000   84.0000  -25.4268 25

 30 omega   19.00   44.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   81.0000    4.7836 25

 31 omega   19.00   44.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   81.0000   73.9934 25

 32 omega   19.00   44.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   80.0000  118.5572 25

 33 omega   19.00   44.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   82.0000  -92.3413 25

 34 omega   19.00   44.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   81.0000  177.0088 25

 35 omega   87.00  146.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   76.0000  139.7882 59

 36 omega   29.00   63.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   76.0000  139.7882 34

 37 omega   29.00   71.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   76.0000  -97.7983 42

 38 omega   29.00   63.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   75.0000   86.2452 34

 39 omega   81.00  107.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   76.0000  -97.7983 26

 40 omega   30.00   62.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   75.0000 -148.9391 32

 41 omega  102.00  146.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   75.0000 -148.9391 44

 42 omega   34.00   71.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   77.0000    9.1794 37

 43 omega   32.00   90.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   77.0000  -42.6809 58

 44 omega  120.00  151.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       72.0000   77.0000  174.3524 31

 45 omega   36.00   75.00   1.0000    1.1000
omega____ theta____ kappa____ phi______ frames
    -       72.0000   77.0000  174.3524 39

 46 omega   74.00  117.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000  120.0000 43

 47 omega  112.00  152.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000  -30.0000 40

 48 omega   74.00  105.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000  -30.0000 31

 49 omega   76.00  115.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000  -60.0000 39

 50 omega  148.00  175.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000 -180.0000 27

 51 omega   74.00   99.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000 -180.0000 25

 52 omega  126.00  171.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000  120.0000 45

 53 omega   79.00  105.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   61.0000   90.0000 26

 54 omega   74.00  100.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000  150.0000 26

 55 omega   78.00  105.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   61.0000 -150.0000 27

 56 omega   74.00  163.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000 -120.0000 89

 57 omega   77.00  104.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   61.0000   60.0000 27

 58 omega   74.00  117.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000   30.0000 43

 59 omega   75.00  102.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000   60.0000 27

 60 omega   78.00  114.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   61.0000   30.0000 36

 61 omega   79.00  145.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   61.0000 -120.0000 66

 62 omega  111.00  138.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000    0.0000 27

 63 omega   75.00  130.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000  -90.0000 55

 64 omega   79.00  106.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   61.0000  -90.0000 27

 65 omega   74.00  100.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000   90.0000 26

 66 omega   74.00   99.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000    0.0000 25

 67 omega   81.00  107.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   61.0000  -60.0000 26

 68 omega   74.00  123.00   1.0000    7.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000 -150.0000 49
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_UB_11      -0.1432262000
_diffrn_orient_matrix_UB_12      -0.0316649000
_diffrn_orient_matrix_UB_13      -0.1039274000
_diffrn_orient_matrix_UB_21      0.0071125000
_diffrn_orient_matrix_UB_22      0.1240844000
_diffrn_orient_matrix_UB_23      0.0223178000
_diffrn_orient_matrix_UB_31      0.1220935000
_diffrn_orient_matrix_UB_32      0.0041665000
_diffrn_orient_matrix_UB_33      -0.0582519000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0256
_diffrn_reflns_av_unetI/netI     0.0186
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       16
_diffrn_reflns_limit_k_min       -16
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -17
_diffrn_reflns_number            22881
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.803
_diffrn_reflns_theta_min         3.477
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.865
_exptl_absorpt_correction_T_max  0.972
_exptl_absorpt_correction_T_min  0.849
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro, Agilent Technologies,
Version 1.171.37.35 (release 13-08-2014 CrysAlis171 .NET)
(compiled Aug 13 2014,18:06:01)
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            red
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.340
_exptl_crystal_description       plate
_exptl_crystal_F_000             616
_exptl_crystal_size_max          0.3089
_exptl_crystal_size_mid          0.1837
_exptl_crystal_size_min          0.0329
_refine_diff_density_max         0.323
_refine_diff_density_min         -0.419
_refine_diff_density_rms         0.040
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.063
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     420
_refine_ls_number_reflns         5761
_refine_ls_number_restraints     127
_refine_ls_restrained_S_all      1.145
_refine_ls_R_factor_all          0.0480
_refine_ls_R_factor_gt           0.0421
_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^)+(0.0596P)^2^+0.4458P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1129
_refine_ls_wR_factor_ref         0.1179
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5022
_reflns_number_total             5761
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6sc00614k2.cif
_cod_data_source_block           spa062
_cod_depositor_comments
'Adding full bibliography for 1543067--1543076.cif.'
_cod_original_cell_volume        1450.56(8)
_cod_database_code               1543071
_chemical_oxdiff_formula         'C31 H36 B F4 N3 O3'
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 F1B-B1 \\sim F1A-B1 \\sim F4B-B1 \\sim F4A-B1 \\sim F3B-B1 \\sim F3A-B1 \\sim
F2A-B1 \\sim F2B-B1
 with sigma of 0.02
 F1A-F2A \\sim F2A-F3A \\sim F3A-F4A \\sim F4A-F1A \\sim F4A-F2A \\sim F3A-F1A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
F2A \\sim F1B \\sim B1 \\sim F2B \\sim F4B \\sim F3B \\sim F3A \\sim F1A \\sim
F4A: within 1A with sigma of 0.04 and sigma for terminal atoms of 0.08
4. Rigid body (RIGU) restrains
 B1, F1A, F2A, F3A, F4A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 B1, F3A, F1A, F2A, F4A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 F1B, F2B, F4B, F3B, B1
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: F1A(0.51613) F2A(0.51613) F3A(0.51613) F4A(0.51613) F1B(0.48387)
 F2B(0.48387) F3B(0.48387) F4B(0.48387)
6.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C26(H26A,H26B), C27(H27A,H27B), C29(H29A,H29B), C30(H30A,H30B),
 C35(H35A,H35B)
6.b Aromatic/amide H refined with riding coordinates:
 N34(H34), C3(H3), C4(H4), C14(H14), C15(H15), C16(H16), C20(H20), C21(H21),
 C22(H22)
6.c Idealised Me refined as rotating group:
 C0AA(H0AA,H0AB,H0AC), C19(H19A,H19B,H19C), C25(H25A,H25B,H25C), C28(H28A,H28B,
 H28C), C31(H31A,H31B,H31C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'