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_1543070
_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         'C30 H33 N2 O4, B F4, C H2 Cl2'
_chemical_formula_sum            'C31 H35 B Cl2 F4 N2 O4'
_chemical_formula_weight         657.32
_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             2015-03-03
_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                82.687(5)
_cell_angle_beta                 66.161(6)
_cell_angle_gamma                79.273(5)
_cell_formula_units_Z            2
_cell_length_a                   10.9867(6)
_cell_length_b                   12.0208(6)
_cell_length_c                   13.2458(8)
_cell_measurement_reflns_used    13462
_cell_measurement_temperature    180.00(14)
_cell_measurement_theta_max      73.5210
_cell_measurement_theta_min      3.6100
_cell_volume                     1569.51(17)
_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      180.00(14)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4679
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.985
_diffrn_measurement_details
;
  1 omega -125.00  -56.40   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865 -178.0000  -60.0000 98

  2 omega -111.00  -27.00   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865  -37.0000 -150.0000 120

  3 omega  -63.00   37.10   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865   57.0000    0.0000 143

  4 omega  -50.00   37.50   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865   37.0000  150.0000 125

  5 omega  -62.00  -22.10   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865   57.0000 -120.0000 57

  6 omega   98.00  127.40   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -       37.6865 -178.0000  -60.0000 42

  7 omega   25.00   51.60   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  -94.0000 -150.0000 38

  8 omega  105.00  168.00   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  111.0000   60.0000 90

  9 omega   73.00  114.30   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999 -111.0000   90.0000 59

 10 omega   31.00  112.90   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999 -111.0000    0.0000 117

 11 omega   32.00   96.40   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  -45.0000   60.0000 92

 12 omega   75.00  173.70   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   30.0000   60.0000 141

 13 omega   62.00  100.50   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  -94.0000 -120.0000 55

 14 omega   72.00  131.50   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   30.0000 -150.0000 85

 15 omega   45.00  134.60   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  -61.0000  -30.0000 128

 16 omega   74.00  108.30   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  -94.0000   90.0000 49

 17 omega   35.00   62.30   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  -94.0000   90.0000 39

 18 omega   49.00  108.50   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  -94.0000 -180.0000 85

 19 omega   34.00   94.90   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999  -45.0000 -180.0000 87

 20 omega   94.00  176.60   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   61.0000  120.0000 118

 21 omega    9.00   35.60   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -       37.6865   72.0000   63.0000 38

 22 omega  -50.00  -17.10   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865  -37.0000   30.0000 47

 23 omega -112.00  -72.80   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865  -37.0000   30.0000 56

 24 omega -113.00  -72.40   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865  -57.0000    0.0000 58

 25 omega  -45.00   -7.90   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -      -37.6865  -57.0000    0.0000 53

 26 omega   74.00  118.10   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -       37.6865   72.0000   63.0000 63

 27 omega   58.00   98.60   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -       37.6865  178.0000    0.0000 58

 28 omega   -3.00   22.20   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -       40.0000   95.0000  109.6720 36

 29 omega    9.00   34.20   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -       48.0000   86.0000   11.2853 36

 30 omega   15.00   40.90   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   80.0000  -72.0821 37

 31 omega   15.00   40.90   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   82.0000   46.0492 37

 32 omega   15.00   40.90   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   82.0000  137.5553 37

 33 omega   15.00   40.90   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -       52.0000   80.0000 -135.2123 37

 34 omega   96.00  121.90   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   82.0000  -51.8527 37

 35 omega   19.00   44.20   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   81.0000  112.4673 36

 36 omega   37.00  105.60   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   76.0000  112.7614 98

 37 omega   29.00   70.30   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   76.0000  170.8690 59

 38 omega  107.00  146.90   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   77.0000   -6.1346 57

 39 omega   28.00   57.40   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   77.0000   39.2400 42

 40 omega   30.00   56.60   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   77.0000   -6.1346 38

 41 omega   32.00   80.30   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   75.0000   82.4939 69

 42 omega   36.00   68.20   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   76.0000  -52.9543 46

 43 omega   36.00   73.10   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -       72.0000   77.0000 -144.6785 53

 44 omega   36.00   71.00   0.7000    0.7000
omega____ theta____ kappa____ phi______ frames
    -       72.0000   76.0000  -88.6017 50

 45 omega   75.00  101.60   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000  120.0000 38

 46 omega  118.00  165.60   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000  -60.0000 68

 47 omega  103.00  138.00   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000 -120.0000 50

 48 omega   74.00  100.60   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000  -60.0000 38

 49 omega   75.00  101.60   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000 -120.0000 38

 50 omega   74.00  111.10   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000   90.0000 53

 51 omega  124.00  160.40   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000 -180.0000 52

 52 omega   74.00  154.50   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000 -150.0000 115

 53 omega   74.00  100.60   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000 -180.0000 38

 54 omega   74.00  133.50   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000    0.0000 85

 55 omega   77.00  111.30   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   61.0000  -30.0000 49

 56 omega   78.00  105.30   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   61.0000  120.0000 39

 57 omega  129.00  154.90   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000  150.0000 37

 58 omega   77.00  104.30   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   61.0000  150.0000 39

 59 omega   74.00  100.60   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000  150.0000 38

 60 omega   77.00  103.60   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   61.0000    0.0000 38

 61 omega   74.00  149.60   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000  -90.0000 108

 62 omega   78.00  104.60   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   61.0000   60.0000 38

 63 omega   74.00  109.00   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000   60.0000 50

 64 omega   74.00  100.60   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000   30.0000 38

 65 omega   76.00  165.60   0.7000    6.0000
omega____ theta____ kappa____ phi______ frames
    -      110.3999   77.0000  -30.0000 128
;
_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      0.1285345000
_diffrn_orient_matrix_UB_12      0.0185863000
_diffrn_orient_matrix_UB_13      -0.1022743000
_diffrn_orient_matrix_UB_21      -0.0460839000
_diffrn_orient_matrix_UB_22      0.1291074000
_diffrn_orient_matrix_UB_23      0.0028183000
_diffrn_orient_matrix_UB_31      0.0733852000
_diffrn_orient_matrix_UB_32      0.0075515000
_diffrn_orient_matrix_UB_33      0.0758603000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0278
_diffrn_reflns_av_unetI/netI     0.0192
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            24305
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         73.622
_diffrn_reflns_theta_min         3.654
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    2.407
_exptl_absorpt_correction_T_max  0.909
_exptl_absorpt_correction_T_min  0.597
_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    1.391
_exptl_crystal_description       plate
_exptl_crystal_F_000             684
_exptl_crystal_size_max          0.303
_exptl_crystal_size_mid          0.192
_exptl_crystal_size_min          0.0406
_refine_diff_density_max         0.682
_refine_diff_density_min         -0.627
_refine_diff_density_rms         0.052
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.067
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     402
_refine_ls_number_reflns         6249
_refine_ls_number_restraints     0
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0545
_refine_ls_R_factor_gt           0.0502
_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^)+(0.0654P)^2^+1.0146P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1320
_refine_ls_wR_factor_ref         0.1362
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5628
_reflns_number_total             6249
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6sc00614k2.cif
_cod_data_source_block           spa041
_cod_depositor_comments
'Adding full bibliography for 1543067--1543076.cif.'
_cod_database_code               1543070
_chemical_oxdiff_formula         'C31 H35 B1 Cl2 F4 N2 O4'
_reflns_odcompleteness_completeness 99.96
_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
 At 1.5 times of:
  All C(H,H,H) groups
2.a Secondary CH2 refined with riding coordinates:
 C25(H25A,H25B), C27(H27A,H27B), C28(H28A,H28B), C30(H30A,H30B), C31(H31A,
 H31B), C40(H,HA)
2.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C11(H11), C12(H12), C13(H13), C20(H20), C21(H21)
2.c Idealised Me refined as rotating group:
 C2AA(H2AA,H2AB,H2AC), C26(H26A,H26B,H26C), C29(H29A,H29B,H29C), C32(H32A,H32B,
 H32C), C34(H34A,H34B,H34C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'