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_1543072
_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         'C32 H38 N3 O3, 0.5(C7 H8), B F4'
_chemical_formula_sum            'C35.5 H42 B F4 N3 O3'
_chemical_formula_weight         645.53
_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             2015-09-03
_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                115.683(3)
_cell_angle_beta                 92.594(3)
_cell_angle_gamma                112.243(3)
_cell_formula_units_Z            2
_cell_length_a                   11.0563(3)
_cell_length_b                   13.2880(4)
_cell_length_c                   14.0408(5)
_cell_measurement_reflns_used    12382
_cell_measurement_temperature    180.00(14)
_cell_measurement_theta_max      73.2210
_cell_measurement_theta_min      4.0740
_cell_volume                     1665.64(12)
_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 0.998
_diffrn_measured_fraction_theta_max 0.986
_diffrn_measurement_details
;
  1 omega  -34.00   -7.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.9365  -57.0000  -60.0000 27

  2 omega  -49.00   39.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.9365   38.0000   90.0000 88

  3 omega    5.00   30.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       44.0000   88.0000   28.3284 25

  4 omega   19.00   44.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   80.0000   29.3821 25

  5 omega   32.00   58.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   77.0000   43.2387 26

  6 omega   32.00   71.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   76.0000   68.2808 39

  7 omega   95.00  151.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   77.0000   43.2387 56

  8 omega  124.00  149.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       68.0000   76.0000   68.2808 25

  9 omega  109.00  135.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       60.0000   76.0000  133.2011 26

 10 omega  117.00  178.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000   60.0000 61

 11 omega  148.00  178.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000    0.0000 30

 12 omega  123.00  148.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       72.0000   75.0000 -102.9079 25

 13 omega  113.00  139.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000  -60.0000 26

 14 omega  111.00  178.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000 -150.0000 67

 15 omega   91.00  120.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   75.0000  -41.2268 29

 16 omega   74.00  100.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000  -60.0000 26

 17 omega   79.00  106.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   61.0000  -60.0000 27

 18 omega   77.00  134.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   61.0000  -30.0000 57

 19 omega   80.00  107.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   61.0000 -120.0000 27

 20 omega   75.00  100.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000 -150.0000 25

 21 omega   74.00  149.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000 -120.0000 75

 22 omega   77.00  103.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   61.0000    0.0000 26

 23 omega   75.00  145.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000    0.0000 70

 24 omega  113.00  172.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000  120.0000 59

 25 omega   79.00  115.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   61.0000  150.0000 36

 26 omega   77.00  177.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000   90.0000 100

 27 omega   74.00  100.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000   60.0000 26

 28 omega   74.00  147.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000   30.0000 73

 29 omega   77.00  103.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   61.0000  120.0000 26

 30 omega   77.00  112.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   61.0000   90.0000 35

 31 omega   77.00  103.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   61.0000   60.0000 26

 32 omega   74.00  100.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000  120.0000 26

 33 omega   74.00  150.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000  150.0000 76

 34 omega   75.00  176.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000  -30.0000 101

 35 omega   74.00  153.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000 -180.0000 79

 36 omega   75.00  177.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499   77.0000  -90.0000 102

 37 omega   57.00  118.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       38.9365  178.0000  -60.0000 61

 38 omega   57.00  130.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       38.9365  178.0000   90.0000 73

 39 omega   32.00   58.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   75.0000  -41.2268 26

 40 omega   29.00   65.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   75.0000  -10.2536 36

 41 omega   19.00   44.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   81.0000  -99.7785 25

 42 omega   36.00   90.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       72.0000   75.0000 -102.9079 54

 43 omega   47.00   79.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -       80.0000   57.0000 -128.1854 32

 44 omega   28.00   57.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       64.0000   76.0000 -158.4851 29

 45 omega    9.00   34.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       48.0000   86.0000 -130.9621 25

 46 omega   19.00   44.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   81.0000  -51.7877 25

 47 omega   20.00   45.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       56.0000   79.0000   86.0849 25

 48 omega   25.00   53.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       60.0000   76.0000  133.2011 28

 49 omega   25.00   50.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       60.0000   76.0000  172.1961 25

 50 omega   28.00   89.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -94.0000   60.0000 61

 51 omega   91.00  116.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499 -111.0000   30.0000 25

 52 omega   45.00   87.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499 -111.0000   30.0000 42

 53 omega   35.00  107.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -94.0000  120.0000 72

 54 omega   30.00  109.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -94.0000  -90.0000 79

 55 omega   35.00   91.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -       38.9365 -139.0000 -169.0000 56

 56 omega   23.00  108.00   1.0000    2.0000
omega____ theta____ kappa____ phi______ frames
    -      109.7499  -94.0000 -180.0000 85

 57 omega -117.00   -6.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.9365  -57.0000  150.0000 111

 58 omega -117.00  -36.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.9365  -57.0000  -60.0000 81

 59 omega -123.00   -3.00   1.0000    1.0000
omega____ theta____ kappa____ phi______ frames
    -      -38.9365  -77.0000   60.0000 120
;
_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      0.1029926000
_diffrn_orient_matrix_UB_12      0.0254934000
_diffrn_orient_matrix_UB_13      0.0951215000
_diffrn_orient_matrix_UB_21      -0.0641646000
_diffrn_orient_matrix_UB_22      0.0715848000
_diffrn_orient_matrix_UB_23      0.0821885000
_diffrn_orient_matrix_UB_31      -0.0972669000
_diffrn_orient_matrix_UB_32      -0.1216524000
_diffrn_orient_matrix_UB_33      -0.0039576000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.5418
_diffrn_reflns_av_R_equivalents  0.0282
_diffrn_reflns_av_unetI/netI     0.0186
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.986
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_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            25669
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.986
_diffrn_reflns_theta_full        67.680
_diffrn_reflns_theta_max         73.407
_diffrn_reflns_theta_min         4.116
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.803
_exptl_absorpt_correction_T_max  0.944
_exptl_absorpt_correction_T_min  0.721
_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    1.287
_exptl_crystal_description       plate
_exptl_crystal_F_000             682
_exptl_crystal_size_max          0.5334
_exptl_crystal_size_mid          0.4221
_exptl_crystal_size_min          0.0689
_refine_diff_density_max         0.512
_refine_diff_density_min         -0.327
_refine_diff_density_rms         0.049
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.049
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     531
_refine_ls_number_reflns         6598
_refine_ls_number_restraints     257
_refine_ls_restrained_S_all      1.088
_refine_ls_R_factor_all          0.0631
_refine_ls_R_factor_gt           0.0574
_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^)+(0.1011P)^2^+0.5666P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1675
_refine_ls_wR_factor_ref         0.1748
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5743
_reflns_number_total             6598
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c6sc00614k2.cif
_cod_data_source_block           spa064
_cod_depositor_comments
'Adding full bibliography for 1543067--1543076.cif.'
_cod_original_cell_volume        1665.63(11)
_cod_original_formula_sum        'C35.50 H42 B F4 N3 O3'
_cod_database_code               1543072
_chemical_oxdiff_formula         'C38 H37 B1 F4 N3 O3'
_reflns_odcompleteness_completeness 99.90
_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. Restrained distances
 F2B-B1 \\sim F3-B1 \\sim F4B-B1 \\sim F4-B1 \\sim F3B-B1 \\sim F1-B1 \\sim
F1B-B1
 with sigma of 0.02
 F1-F2 \\sim F1-F3 \\sim F1-F4 \\sim F2-F3 \\sim F2-F4 \\sim F3-F4
 with sigma of 0.04
 N33-C36A \\sim N33-C36
 with sigma of 0.02
 C37A-C36A \\sim C37-C36
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C47 \\sim C48 \\sim C49 \\sim C50 \\sim C51 \\sim C52 \\sim C53 \\sim C40 \\sim
C41 \\sim C42 \\sim C43 \\sim C44 \\sim C45 \\sim C46: within 1.1A with sigma
of 0.04 and sigma for terminal atoms of 0.08
Uanis(C49) = Uanis(C42) = Uanis(C41) = Uanis(C50)
4. Rigid body (RIGU) restrains
 B1, F1B, F2B, F3B, F4B
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 B1, F1, F2, F3, F4
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N33, C37A, C36
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 N33, C36, C37
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C47, C48, C49, C50, C51, C52, C53
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C40, C41, C42, C43, C44, C45, C46
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(F1B)=Sof(F2B)=Sof(F3B)=Sof(F4B)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=Sof(F4)=FVAR(1)
 Sof(C36A)=Sof(H36A)=Sof(H36B)=Sof(C37A)=Sof(H37D)=Sof(H37E)=Sof(H37F)=1-FVAR(2)
 Sof(C36)=Sof(H36C)=Sof(H36D)=Sof(C37)=Sof(H37A)=Sof(H37B)=Sof(H37C)=FVAR(2)
 Fixed Sof: C47(0.25) H47A(0.25) H47B(0.25) H47C(0.25) C48(0.25) C49(0.25)
 H49(0.25) C50(0.25) H50(0.25) C51(0.25) H51(0.25) C52(0.25) H52(0.25)
 C53(0.25) H53(0.25) C40(0.25) H40A(0.25) H40B(0.25) H40C(0.25) C41(0.25)
 C42(0.25) H42(0.25) C43(0.25) H43(0.25) C44(0.25) H44(0.25) C45(0.25)
 H45(0.25) C46(0.25) H46(0.25)
6.a Free rotating group:
 C47(C48,C49,C50,C51,C52,C53), C40(C41,C42,C43,C44,C45,C46,B1,F1,F2,F3,F4,F1B,
 F2B,F3B,F4B)
6.b Secondary CH2 refined with riding coordinates:
 C26(H26A,H26B), C27(H27A,H27B), C28(H28A,H28B), C29(H29A,H29B), C34(H34A,
 H34B), C36A(H36A,H36B), C36(H36C,H36D)
6.c Aromatic/amide H refined with riding coordinates:
 C1(H1), C2(H2), C6(H6), C7(H7), C8(H8), C18(H18), C19(H19), C20(H20),
 C49(H49), C50(H50), C51(H51), C52(H52), C53(H53), C42(H42), C43(H43), C44(H44),
  C45(H45), C46(H46)
6.d Idealised Me refined as rotating group:
 C1AA(H1AA,H1AB,H1AC), C11(H11A,H11B,H11C), C17(H17A,H17B,H17C), C30(H30A,H30B,
 H30C), C35(H35A,H35B,H35C), C37A(H37D,H37E,H37F), C37(H37A,H37B,H37C),
 C47(H47A,H47B,H47C), C40(H40A,H40B,H40C)
;
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'