Reversal of chirality in solutions and aggregates of chiral tetrachlorinated diperylene diimides towards efficient circularly polarized light detection.
Gao, Ke; Lee, Sang Hyuk; Zhao, Wenkai; Ahn, Jaeyong; Kim, Tae Woo; Li, Zhenping; Zhuo, Huagui; Wang, Zhiwei; Zheng, Xinglong; Yan, Yang; Chang, Gang; Ma, Wei; Zhang, Mingming; Long, Guankui; Oh, Joon Hak; Shang, Xiaobo; Materials horizons 12 (2025) 1903–1912; doi:10.1039/d4mh01435a

data_1573419
_publ_section_title
;
 Reversal of chirality in solutions and aggregates of chiral
 tetrachlorinated diperylene diimides towards efficient circularly
 polarized light detection.
;
_journal_issue                   6
_journal_name_full               'Materials horizons'
_journal_page_first              1903
_journal_page_last               1912
_journal_paper_doi               10.1039/d4mh01435a
_journal_volume                  12
_journal_year                    2025
_chemical_absolute_configuration ad
_chemical_formula_moiety         'C80 H66 Cl4 N4 O8, C3 H7 N O, 3[C3H7O]'
_chemical_formula_sum            'C92 H94 Cl4 N5 O12'
_chemical_formula_weight         1603.52
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2024-11-06
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-11-16 deposited with the CCDC.	2024-12-05 downloaded from the CCDC.
;
_cell_angle_alpha                89.652(13)
_cell_angle_beta                 88.476(13)
_cell_angle_gamma                78.232(12)
_cell_formula_units_Z            2
_cell_length_a                   14.924(3)
_cell_length_b                   15.705(3)
_cell_length_c                   17.535(4)
_cell_measurement_reflns_used    5730
_cell_measurement_temperature    193.00
_cell_measurement_theta_max      59.99
_cell_measurement_theta_min      2.63
_cell_volume                     4022.1(15)
_computing_cell_refinement       'SAINT V8.40B (?, 2016)'
_computing_data_collection       'Apex3 (Bruker 2018)'
_computing_data_reduction        'SAINT V8.40B (?, 2016)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      193.00
_diffrn_measured_fraction_theta_full 0.995
_diffrn_measured_fraction_theta_max 0.995
_diffrn_measurement_device_type  'CCD area detector'
_diffrn_measurement_method       'phi and omega scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1240
_diffrn_reflns_av_unetI/netI     0.1712
_diffrn_reflns_Laue_measured_fraction_full 0.995
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -12
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -13
_diffrn_reflns_number            17960
_diffrn_reflns_point_group_measured_fraction_full 0.817
_diffrn_reflns_point_group_measured_fraction_max 0.817
_diffrn_reflns_theta_full        16.500
_diffrn_reflns_theta_max         16.500
_diffrn_reflns_theta_min         1.162
_diffrn_source_current           2.86
_diffrn_source_power             0.19937059999999998
_diffrn_source_voltage           69.71
_exptl_absorpt_coefficient_mu    0.215
_exptl_absorpt_correction_T_max  0.7518
_exptl_absorpt_correction_T_min  0.4212
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1492 before and 0.1060 after correction.
The Ratio of minimum to maximum transmission is 0.5603.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            white
_exptl_crystal_colour_primary    white
_exptl_crystal_density_diffrn    1.324
_exptl_crystal_description       block
_exptl_crystal_F_000             1690
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.15
_exptl_crystal_size_min          0.13
_refine_diff_density_max         0.632
_refine_diff_density_min         -0.388
_refine_diff_density_rms         0.082
_refine_ls_abs_structure_details
;
 Flack x determined using 1212 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.21(14)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1831
_refine_ls_number_reflns         7006
_refine_ls_number_restraints     5202
_refine_ls_restrained_S_all      0.799
_refine_ls_R_factor_all          0.1209
_refine_ls_R_factor_gt           0.0924
_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^)+(0.1912P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2346
_refine_ls_wR_factor_ref         0.2646
_reflns_Friedel_coverage         0.641
_reflns_Friedel_fraction_full    0.638
_reflns_Friedel_fraction_max     0.638
_reflns_number_gt                5196
_reflns_number_total             7006
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4mh01435a2.cif
_cod_data_source_block           zhcz
_cod_depositor_comments          'Adding full bibliography for 1573419.cif.'
_cod_original_cell_volume        4022.1(14)
_cod_database_code               1573419
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.973
_shelx_estimated_absorpt_t_min   0.962
_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
 C44-C43
 1.54 with sigma of 0.01
 N10-C162 = N10-C163 = N9-C164 = N9-C165
 1.48 with sigma of 0.02
 O10-C89
 1.25 with sigma of 0.02
 C124-C125
 1.38 with sigma of 0.02
 N10-C161 = N9-C166
 1.36 with sigma of 0.02
 C87-C86
 1.54 with sigma of 0.02
 C57-C56
 1.54 with sigma of 0.02
 C78-C77 = C158-C157
 1.54 with sigma of 0.02
 C27-C26 = C24-C18 = C44-C43 = C48-C47 = C96-C101
 1.4 with sigma of 0.02
 O15-C136
 1.28 with sigma of 0.02
 C120-C119
 1.4 with sigma of 0.02
 C91-C90
 1.4 with sigma of 0.02
 C47-C38
 1.4 with sigma of 0.02
 C30-C25
 1.4 with sigma of 0.02
 C20-C10
 1.4 with sigma of 0.02
 C127-C126
 1.4 with sigma of 0.02
 C53-C52 = C54-C53 = C55-C54 = C56-C55 = C57-C56 = C57-C52
 1.5 with sigma of 0.01
 C61-C60 = C62-C61 = C63-C62 = C64-C63 = C65-C64 = C65-C60
 1.5 with sigma of 0.01
 C75-C74 = C79-C74 = C79-C78 = C78-C77 = C77-C76 = C76-C75
 1.5 with sigma of 0.01
 C6-C5 = C6-C1 = C2-C1 = C3-C2 = C4-C3 = C5-C4
 1.5 with sigma of 0.01
 C149-C126 \\sim C126-C125
 with sigma of 0.02
 C142-C141 \\sim C143-C142 \\sim C144-C143 \\sim C145-C144 \\sim C145-C140
\\sim C141-C140
 with sigma of 0.02
 C83-C82 \\sim C82-C81 \\sim C86-C81 \\sim C86-C85 \\sim C85-C84 \\sim C84-C83
 with sigma of 0.02
 C160-C155 \\sim C160-C159 \\sim C159-C158 \\sim C158-C157 \\sim C157-C156
\\sim C156-C155
 with sigma of 0.02
 C116-C115 \\sim C115-C114 \\sim C114-C113 \\sim C113-C112 \\sim C112-C111
\\sim C116-C111
 with sigma of 0.02
 C95-C94 \\sim C96-C95 \\sim C97-C96 \\sim C97-C91 \\sim C92-C91 \\sim C94-C92
 with sigma of 0.02
 C97-C91 \\sim C91-C90 \\sim C90-C122 \\sim C122-C121 \\sim C98-C97 \\sim
C98-C121
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C155 \\sim C156 \\sim C157 \\sim C158 \\sim C159 \\sim C160: within 3A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 3A
C89 \\sim C90 \\sim C91 \\sim C92 \\sim C93 \\sim N5: within 3A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 3A
C106 \\sim C117 \\sim C107 \\sim C105 \\sim C104 \\sim C108: within 3A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 3A
C27 \\sim C28 \\sim C29 \\sim C30 \\sim C25 \\sim C26: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
C81 \\sim C82 \\sim C83 \\sim C84 \\sim C85 \\sim C86: within 3A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 3A
C131 \\sim Cl7 \\sim C130 \\sim C128 \\sim C129 \\sim C127 \\sim C132 \\sim
C124 \\sim C133 \\sim C146 \\sim C126 \\sim C137 \\sim C123 \\sim C125 \\sim
C134 \\sim Cl8 \\sim C147 \\sim C149 \\sim O16 \\sim N8 \\sim C122 \\sim C135
\\sim C120 \\sim C136 \\sim C148 \\sim C150 \\sim C138 \\sim C90 \\sim C121
\\sim C119 \\sim O15 \\sim C152 \\sim C151 \\sim C139 \\sim C140 \\sim C89
\\sim C91 \\sim C98 \\sim C118 \\sim O14 \\sim N7 \\sim O13 \\sim C141 \\sim
C145 \\sim N5 \\sim O10 \\sim C92 \\sim C97 \\sim C99 \\sim C117 \\sim C153
\\sim C142 \\sim C144 \\sim C93 \\sim C87 \\sim C94 \\sim C96 \\sim C100 \\sim
C106 \\sim C155 \\sim C154 \\sim C143 \\sim O9 \\sim C86 \\sim C88 \\sim C95
\\sim C101 \\sim C105 \\sim C107 \\sim C160 \\sim C156 \\sim C81 \\sim C85
\\sim Cl5 \\sim C102 \\sim C104 \\sim N6 \\sim O12 \\sim C159 \\sim C157 \\sim
C82 \\sim C84 \\sim Cl6 \\sim C103 \\sim C108 \\sim C109 \\sim C158 \\sim C83
\\sim O11 \\sim C111 \\sim C110 \\sim C112 \\sim C116 \\sim C113 \\sim C115
\\sim C114: within 3A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 3A
C48 \\sim Cl1 \\sim C15 \\sim C16 \\sim C14 \\sim C17 \\sim C26 \\sim C12 \\sim
C11 \\sim C18 \\sim C27 \\sim C25 \\sim C13 \\sim C10 \\sim C24 \\sim C19 \\sim
Cl2 \\sim C28 \\sim C30 \\sim O1 \\sim N1 \\sim C9 \\sim C20 \\sim C23 \\sim
C21 \\sim C29 \\sim C31 \\sim C7 \\sim O2 \\sim C22 \\sim C34 \\sim C70 \\sim
C33 \\sim C32 \\sim C6 \\sim C8 \\sim C41 \\sim C35 \\sim C69 \\sim C71 \\sim
O3 \\sim N2 \\sim O4 \\sim C1 \\sim C5 \\sim C40 \\sim C42 \\sim C36 \\sim O8
\\sim N4 \\sim C67 \\sim C59 \\sim C2 \\sim C4 \\sim C39 \\sim C43 \\sim C37
\\sim C68 \\sim C73 \\sim C66 \\sim C60 \\sim C58 \\sim C3 \\sim C44 \\sim C38
\\sim C80 \\sim C49 \\sim O7 \\sim C74 \\sim C72 \\sim C61 \\sim C65 \\sim C45
\\sim C47 \\sim Cl3 \\sim O5 \\sim N3 \\sim C75 \\sim C79 \\sim C62 \\sim C64
\\sim Cl4 \\sim C46 \\sim C50 \\sim C76 \\sim C78 \\sim C63 \\sim O6 \\sim C52
\\sim C51 \\sim C77 \\sim C57 \\sim C53 \\sim C56 \\sim C54 \\sim C55: within
3A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 3A
Uanis(C89) \\sim Ueq, Uanis(C154) \\sim Ueq, Uanis(C57) \\sim Ueq, Uanis(C58)
\\sim Ueq, Uanis(C143) \\sim Ueq, Uanis(C62) \\sim Ueq, Uanis(C83) \\sim Ueq:
with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C89) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C154) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C158) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O18) \\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C163) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C153) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C164) \\sim Ueq, Uanis(N9) \\sim Ueq, Uanis(C165) \\sim Ueq, Uanis(C166)
\\sim Ueq: with sigma of 0.02 and sigma for terminal atoms of 0.04
Uanis(C41) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C73) \\sim Ueq, Uanis(C39)
\\sim Ueq, Uanis(C87) \\sim Ueq, Uanis(C86) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C144, C143, C142, C141, C140, C145
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 O17, N10, C161, C163, C162
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
 C63, C62, C64, C65, C60, C61
 with sigma for 1-2 distances of 0.05 and sigma for 1-3 distances of 0.01
 C74, C73
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C61, C60, C65, C64, C63, C62
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C150, C119, C120, C125, C149
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C95, C96, C97, C91, C92, C94
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C146, C149, C148, C147
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C74, C73, C72, C75, C79, C76, C77, C78
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
 C6, C5
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.01
5.a Ternary CH refined with riding coordinates:
 C87(H87), C7(H7), C6(H6), C111(H111), C138(H138), C73(H73), C60(H60),
 C109(H109), C59(H59), C74(H74), C50(H50), C52(H52), C86(H86), C140(H140),
 C153(H153), C155(H155)
5.b Secondary CH2 refined with riding coordinates:
 C81(H81A,H81B), C3(H3A,H3B), C1(H1A,H1B), C77(H77A,H77B), C114(H11D,H11E),
 C160(H16A,H16B), C113(H11F,H11G), C141(H14A,H14B), C76(H76A,H76B), C75(H75A,
 H75B), C57(H57A,H57B), C112(H11H,H11I), C115(H11J,H11K), C54(H54A,H54B),
 C56(H56A,H56B), C61(H61A,H61B), C116(H11L,H11M), C2(H2A,H2B), C4(H4A,H4B),
 C142(H14C,H14D), C159(H15D,H15E), C144(H14E,H14F), C78(H78A,H78B), C82(H82A,
 H82B), C85(H85A,H85B), C157(H15F,H15G), C156(H15H,H15I), C63(H63A,H63B),
 C158(H15J,H15K), C64(H64A,H64B), C65(H65A,H65B), C5(H5A,H5B), C53(H53A,H53B),
 C55(H55A,H55B), C143(H14G,H14H), C79(H79A,H79B), C145(H14I,H14J), C62(H62A,
 H62B), C84(H84A,H84B), C83(H83A,H83B)
5.c Aromatic/amide H refined with riding coordinates:
 C147(H147), C36(H36), C103(H103), C28(H28), C20(H20), C66(H66), C135(H135),
 C14(H14), C131(H131), C117(H117), C94(H94), C46(H46), C161(H161), C166(H166)
5.d Idealised Me refined as rotating group:
 C110(H11A,H11B,H11C), C154(H15A,H15B,H15C), C88(H88A,H88B,H88C), C139(H13A,
 H13B,H13C), C8(H8A,H8B,H8C), C58(H58A,H58B,H58C), C72(H72A,H72B,H72C),
 C51(H51A,H51B,H51C), C163(H16C,H16D,H16E), C165(H16I,H16J,H16K), C162(H16F,
 H16G,H16H), C164(H16L,H16M,H16N)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 212 electrons were 
found in a volume of 888\%A^3^ in 1 void per unit cell. 
This is consistent with the presence of 
6[C3H7O] per formula unit 
which account for 198 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              45463
_shelx_fab_checksum              62510
_olex2_submission_special_instructions 'No special instructions were received'