Aggregation-induced Chirality Amplification of Optically Active Fluorescent Polyurethane and Cyclic Dimer in the Ground and Excited States
Song, Zhiyi; Sato, Hiroyasu; Pietropaolo, Adriana; Wang, Qingyu; Shimoda, Shuhei; Dai, Heshuang; Imai, Yoshitane; Toda, Hayato; Harada, Takunori; Shichibu, Yukatsu; Konishi, Katsuaki; Bando, Masayoshi; Naga, Naofumi; Nakano, Tamaki; Chemical Communications  (2021) –; doi:10.1039/D1CC05633F

data_7129354
_publ_section_title
;
 Aggregation-induced Chirality Amplification of Optically Active
 Fluorescent Polyurethane and Cyclic Dimer in the Ground and Excited
 States
;
_journal_name_full               'Chemical Communications'
_journal_paper_doi               10.1039/D1CC05633F
_journal_year                    2021
_chemical_absolute_configuration rmad
_chemical_formula_moiety         'C70 H44 N4 O8, 6(C4 H8 O)'
_chemical_formula_sum            'C94 H92 N4 O14'
_chemical_formula_weight         1501.71
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2021-04-23
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6272)
;
_audit_update_record
;
2021-08-31 deposited with the CCDC.	2021-12-07 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   10.27320(10)
_cell_length_b                   26.8858(3)
_cell_length_c                   28.5990(3)
_cell_measurement_reflns_used    24853
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      73.3200
_cell_measurement_theta_min      2.2490
_cell_volume                     7899.14(14)
_computing_cell_refinement       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.105a (Rigaku OD, 2021)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Rigaku HyPix-6000 area detector'
_diffrn_detector_area_resol_mean 10.0
_diffrn_detector_type            'HPC area detector'
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.992
_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     63.00 114.00   0.50    3.83    --   41.73 149.00-178.00  102
  2  \w   -175.00 -79.00   0.50   15.32    -- -104.00-118.00  25.00  192
  3  \w     55.00 178.00   0.50   15.32    --  114.50  12.00 -58.00  246
  4  \w     41.00 129.00   0.50   15.32    --  114.50-149.00 134.00  176
  5  \w    -23.00  39.00   0.50    3.83    --  -41.73  19.00  30.00  124
  6  \w    -21.00  39.00   0.50    3.83    --  -41.73  12.00 -58.00  120
  7  \w    -38.00  27.00   0.50    3.83    --   41.73 -12.00 129.00  130
  8  \w     18.00  95.00   0.50    3.83    --   41.73-125.00 150.00  154
  9  \w     17.00  94.00   0.50    3.83    --   41.73-123.00 -61.00  154
 10  \w     40.00 108.00   0.50   15.32    --  114.50-111.00  30.00  136
 11  \w     41.00  74.00   0.50   15.32    --  114.50 -61.00-180.00   66
 12  \w     41.00  74.00   0.50   15.32    --  114.50 -61.00   0.00   66
 13  \w     41.00  74.00   0.50   15.32    --  114.50 -61.00-150.00   66
 14  \w     40.00 108.00   0.50   15.32    --  114.50-111.00 -30.00  136
 15  \w     64.00 178.00   0.50   15.32    --  114.50  15.00  60.00  228
 16  \w     41.00  74.00   0.50   15.32    --  114.50 -61.00  90.00   66
 17  \w     41.00  74.00   0.50   15.32    --  114.50 -61.00 150.00   66
 18  \w     41.00 108.00   0.50   15.32    --  114.50 -77.00  60.00  134
 19  \w     92.00 178.00   0.50   15.32    --  114.50  45.00-180.00  172
 20  \w     40.00 108.00   0.50   15.32    --  114.50-111.00  60.00  136
 21  \w     41.00 105.00   0.50   15.32    --  114.50 -95.00   0.00  128
 22  \w     40.00 108.00   0.50   15.32    --  114.50-111.00   0.00  136
 23  \w     41.00 105.00   0.50   15.32    --  114.50 -95.00-120.00  128
 24  \w     41.00  74.00   0.50   15.32    --  114.50 -61.00  60.00   66
 25  \w   -115.00 -13.00   0.50    3.83    --  -41.73 -77.00 150.00  204
 26  \w   -115.00 -13.00   0.50    3.83    --  -41.73 -77.00  30.00  204
 27  \w   -115.00 -13.00   0.50    3.83    --  -41.73 -77.00 -90.00  204
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB Synergy-R'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0203618000
_diffrn_orient_matrix_UB_12      -0.0529571000
_diffrn_orient_matrix_UB_13      -0.0192636000
_diffrn_orient_matrix_UB_21      0.0144756000
_diffrn_orient_matrix_UB_22      0.0212547000
_diffrn_orient_matrix_UB_23      -0.0497263000
_diffrn_orient_matrix_UB_31      0.1478771000
_diffrn_orient_matrix_UB_32      0.0052055000
_diffrn_orient_matrix_UB_33      0.0075766000
_diffrn_radiation_monochromator  'multi-layer mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0622
_diffrn_reflns_av_unetI/netI     0.0403
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.992
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       33
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            83273
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         79.228
_diffrn_reflns_theta_min         2.255
_diffrn_source                   'rotating anode X-ray generator'
_diffrn_source_type              PhotonJet-R
_exptl_absorpt_coefficient_mu    0.682
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.64472
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.105a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.263
_exptl_crystal_description       needle
_exptl_crystal_F_000             3184
_exptl_crystal_size_max          0.193
_exptl_crystal_size_mid          0.043
_exptl_crystal_size_min          0.035
_refine_diff_density_max         0.459
_refine_diff_density_min         -0.286
_refine_diff_density_rms         0.055
_refine_ls_abs_structure_details
;
 Flack x determined using 4870 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.11(8)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.048
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1052
_refine_ls_number_reflns         16842
_refine_ls_number_restraints     497
_refine_ls_restrained_S_all      1.044
_refine_ls_R_factor_all          0.0871
_refine_ls_R_factor_gt           0.0726
_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^)+(0.1550P)^2^+0.8845P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2140
_refine_ls_wR_factor_ref         0.2313
_reflns_Friedel_coverage         0.808
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.975
_reflns_number_gt                13225
_reflns_number_total             16842
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1cc05633f2.cif
_cod_data_source_block           27dib-s-binol-dimer_2
_cod_database_code               7129354
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C95 H68 N4 O13'
_shelx_estimated_absorpt_t_max   0.977
_shelx_estimated_absorpt_t_min   0.880
_reflns_odcompleteness_completeness 99.98
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups, All N(H) groups
2. Restrained distances
 O14-C94 = O14-C91
 1.43 with sigma of 0.01
 O14A-C91A = O14A-C94A
 1.43 with sigma of 0.01
 C92-C91 = C93-C92 = C94-C93
 1.52 with sigma of 0.01
 C94A-C93A = C93A-C92A = C92A-C91A
 1.52 with sigma of 0.01
 O14-C93
 2.37 with sigma of 0.01
 O14-C92
 2.37 with sigma of 0.01
 O14A-C93A
 2.37 with sigma of 0.01
 O14A-C92A
 2.37 with sigma of 0.01
 C91-C94
 2.32 with sigma of 0.01
 C91A-C94A
 2.32 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
O14 \\sim C91 \\sim C94 \\sim C93 \\sim C92: within 2A with sigma of 0.02 and
sigma for terminal atoms of 0.04 within 2A
O14A \\sim C91A \\sim C93A \\sim C94A \\sim C92A: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
C76 \\sim C78 \\sim C75 \\sim C77 \\sim O10: within 2A with sigma of 0.04 and
sigma for terminal atoms of 0.08 within 2A
C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C20 \\sim C19 \\sim C18 \\sim
C17 \\sim C16: within 2A with sigma of 0.04 and sigma for terminal atoms of
0.08 within 2A
O9 \\sim C74 \\sim C71 \\sim C71A \\sim C73 \\sim C73A \\sim C72 \\sim C72A:
within 2A with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
O13 \\sim C90 \\sim C87 \\sim C89 \\sim C89A \\sim C88 \\sim C88A: within 2A
with sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
4. Rigid body (RIGU) restrains
 C76, C78, C75, C77, O10
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C11, C12, C13, C14, C15, C16, C17, C18, C19, C20
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O9, C74, C71, C71A, C73, C73A, C72, C72A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O13, C90, C87, C89, C89A, C88, C88A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(H74C)=Sof(H74D)=Sof(C71A)=Sof(H71C)=Sof(H71D)=Sof(C72A)=Sof(H72C)=
 Sof(H72D)=Sof(C73A)=Sof(H73C)=Sof(H73D)=1-FVAR(1)
 Sof(H74A)=Sof(H74B)=Sof(C73)=Sof(H73A)=Sof(H73B)=Sof(C71)=Sof(H71A)=Sof(H71B)=
 Sof(C72)=Sof(H72A)=Sof(H72B)=FVAR(1)
 Sof(H90C)=Sof(H90D)=Sof(H87C)=Sof(H87D)=Sof(C89A)=Sof(H89C)=Sof(H89D)=
 Sof(C88A)=Sof(H88C)=Sof(H88D)=1-FVAR(2)
 Sof(H90A)=Sof(H90B)=Sof(H87A)=Sof(H87B)=Sof(C89)=Sof(H89A)=Sof(H89B)=Sof(C88)=
 Sof(H88A)=Sof(H88B)=FVAR(2)
 Sof(O14A)=Sof(C91A)=Sof(H91C)=Sof(H91D)=Sof(C92A)=Sof(H92C)=Sof(H92D)=
 Sof(C93A)=Sof(H93C)=Sof(H93D)=Sof(C94A)=Sof(H94C)=Sof(H94D)=1-FVAR(3)
 Sof(O14)=Sof(C92)=Sof(H92A)=Sof(H92B)=Sof(C91)=Sof(H91A)=Sof(H91B)=Sof(C94)=
 Sof(H94A)=Sof(H94B)=Sof(C93)=Sof(H93A)=Sof(H93B)=FVAR(3)
6.a Secondary CH2 refined with riding coordinates:
 C57(H57A,H57B), C70(H70A,H70B), C79(H79A,H79B), C82(H82A,H82B), C74(H74A,
 H74B), C74(H74C,H74D), C81(H81A,H81B), C80(H80A,H80B), C83(H83A,H83B),
 C73(H73A,H73B), C86(H86A,H86B), C76(H76A,H76B), C71(H71A,H71B), C84(H84A,H84B),
  C90(H90A,H90B), C90(H90C,H90D), C77(H77A,H77B), C87(H87A,H87B), C87(H87C,
 H87D), C85(H85A,H85B), C78(H78A,H78B), C75(H75A,H75B), C72(H72A,H72B),
 C89(H89A,H89B), C88(H88A,H88B), C71A(H71C,H71D), C72A(H72C,H72D), C73A(H73C,
 H73D), C89A(H89C,H89D), C88A(H88C,H88D), C92(H92A,H92B), C91(H91A,H91B),
 C94(H94A,H94B), C93(H93A,H93B), C91A(H91C,H91D), C92A(H92C,H92D), C93A(H93C,
 H93D), C94A(H94C,H94D)
6.b Aromatic/amide H refined with riding coordinates:
 N4(H4), N1(H1), N3(H3), C53(H53), N2(H2), C47(H47), C3(H3A), C50(H50),
 C69(H69), C63(H63), C49(H49), C66(H66), C35(H35), C36(H36), C55(H55), C62(H62),
  C60(H60), C68(H68), C4(H4A), C56(H56), C6(H6), C25(H25), C41(H41), C38(H38),
 C9(H9), C40(H40), C39(H39), C26(H26), C28(H28), C16(H16), C8(H8), C19(H19),
 C31(H31), C7(H7), C13(H13), C18(H18), C17(H17), C14(H14), C29(H29), C30(H30)
;
_shelx_res_checksum              38106
_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 1.566
_oxdiff_exptl_absorpt_empirical_full_min 0.590