CPL on/off switching by enantiomer encapsulation in TPE heterochiral molecular cages.
Yu, Wei; Hu, Ming; Wen, Xin; Xu, Zhi-Rong; Liu, Minghua; Zheng, Yan-Song; Chemical science 16 (2025) 20924–20930; doi:10.1039/d5sc05405b

data_1575910
_publ_section_title
;
 CPL on/off switching by enantiomer encapsulation in TPE heterochiral
 molecular cages.
;
_journal_issue                   44
_journal_name_full               'Chemical science'
_journal_page_first              20924
_journal_page_last               20930
_journal_paper_doi               10.1039/d5sc05405b
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety
'8(F6 P), 20(C4 H8 O2), 2(H2 O), C140 H128 N8, C2 H3 N'
_chemical_formula_sum            'C222 H295 F48 N9 O42 P8'
_chemical_formula_weight         4921.41
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-06-21
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2025-05-23 deposited with the CCDC.	2025-09-26 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.6020(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   18.6896(2)
_cell_length_b                   39.6256(4)
_cell_length_c                   31.8611(4)
_cell_measurement_reflns_used    42024
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      74.0050
_cell_measurement_theta_min      2.6470
_cell_volume                     23549.3(5)
_computing_cell_refinement       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.39.28b (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.997
_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    -21.00  31.00   0.50    1.00    --    0.00 -82.00 -30.00  104
  2  \w     43.00  69.00   0.50    1.00    --    0.00  57.00  30.00   52
  3  \w    -21.00   4.00   0.50    1.00    --    0.00  57.00  30.00   50
  4  \w    -30.00  31.00   0.50    1.00    --    0.00 -82.00-150.00  122
  5  \w    -30.00   1.00   0.50    1.00    --    0.00 -82.00 120.00   62
  6  \w     89.00 181.00   0.50    4.00    --   95.20  30.00-120.00  184
  7  \w     86.00 127.00   0.50    4.00    --   95.20 -82.00 -30.00   82
  8  \w     81.00 119.00   0.50    4.00    --   95.20 -61.00  30.00   76
  9  \w     85.00 120.00   0.50    4.00    --   95.20 -82.00  90.00   70
 10  \w      9.00  51.00   0.50    4.00    --   95.20 -45.00  60.00   84
 11  \w     72.00 134.00   0.50    4.00    --   95.20  61.00-180.00  124
 12  \w     17.00  43.00   0.50    4.00    --   95.20 -77.00 120.00   52
 13  \w     54.00  85.00   0.50    4.00    --   95.20 -77.00 120.00   62
 14  \w      6.00 127.00   0.50    4.00    --   95.20 -82.00  30.00  242
 15  \w     16.00  67.00   0.50    4.00    --   95.20 -61.00  30.00  102
 16  \w     29.00 106.00   0.50    4.00    --   95.20 -15.00  60.00  154
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB AFC12 (RINC): Kappa single'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0164616000
_diffrn_orient_matrix_UB_12      0.0019573000
_diffrn_orient_matrix_UB_13      -0.0479257000
_diffrn_orient_matrix_UB_21      -0.0089776000
_diffrn_orient_matrix_UB_22      -0.0386385000
_diffrn_orient_matrix_UB_23      -0.0017578000
_diffrn_orient_matrix_UB_31      -0.0804310000
_diffrn_orient_matrix_UB_32      0.0038772000
_diffrn_orient_matrix_UB_33      0.0068650000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0664
_diffrn_reflns_av_unetI/netI     0.0661
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.997
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       30
_diffrn_reflns_limit_k_min       -47
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            133030
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.997
_diffrn_reflns_theta_full        67.499
_diffrn_reflns_theta_max         67.499
_diffrn_reflns_theta_min         2.618
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.519
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.68570
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.28b (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.388
_exptl_crystal_description       plank
_exptl_crystal_F_000             10312
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.22
_exptl_crystal_size_min          0.08
_refine_diff_density_max         1.477
_refine_diff_density_min         -0.757
_refine_diff_density_rms         0.103
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     3384
_refine_ls_number_reflns         42336
_refine_ls_number_restraints     1540
_refine_ls_restrained_S_all      1.056
_refine_ls_R_factor_all          0.1222
_refine_ls_R_factor_gt           0.1002
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1837P)^2^+39.1694P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2864
_refine_ls_wR_factor_ref         0.3079
_reflns_Friedel_coverage         0.000
_reflns_number_gt                30912
_reflns_number_total             42336
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc05405b2.cif
_cod_data_source_block           20240621_yw-1
_cod_depositor_comments
'Adding full bibliography for 1575910--1575911.cif.'
_cod_database_code               1575910
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.888
_shelx_estimated_absorpt_t_min   0.517
_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
 At 1.5 times of:
  All C(H,H,H) groups, All O(H,H) groups
2. Restrained distances
 C27A-C1E = C1D-C226
 1.5 with sigma of 0.02
 C1E-O19A = O19A-C1D
 1.4 with sigma of 0.02
 C27A-O35 = O35-C226
 1.4 with sigma of 0.02
 C1D-C1E
 2.4 with sigma of 0.02
 C1G-O33A = O33A-C1H
 1.4 with sigma of 0.02
 C1G-C1H
 2.4 with sigma of 0.02
 C1F-O31A = O31A-C227
 1.4 with sigma of 0.02
 C227-C1H
 1.5 with sigma of 0.02
 C95A-C25A
 1.5 with sigma of 0.02
 C228-C3A
 1.5 with sigma of 0.02
 C228-O13A = O13A-C95A
 1.4 with sigma of 0.02
 O5A-C229 = O41A-C1J
 1.4 with sigma of 0.02
 O41A-C1I = C55A-O5A
 1.4 with sigma of 0.02
 O41A-C229 = O5A-C1J
 2.4 with sigma of 0.02
 C221-C219
 2.4 with sigma of 0.02
 C228-C95A
 2.4 with sigma of 0.02
 C55-O41
 2.4 with sigma of 0.02
 C221-O5
 2.4 with sigma of 0.02
 C55-C221
 1.5 with sigma of 0.02
 C55A-C1J
 1.5 with sigma of 0.02
 H252_$1-H58
 2.2 with sigma of 0.01
 H59-H55
 2 with sigma of 0.02
 O42-C41 \\sim O42A-C41A
 with sigma of 0.02
 O42-C23 \\sim O42A-C23A
 with sigma of 0.02
 O7-C93 \\sim O7A-C93
 with sigma of 0.02
 O7-C199 \\sim O7A-C199
 with sigma of 0.02
 C41-C93 \\sim C41A-C93
 with sigma of 0.02
 C23-C199 \\sim C23A-C199
 with sigma of 0.02
 O42-C93 \\sim O42A-C93
 with sigma of 0.04
 O42-C199 \\sim O42A-C199
 with sigma of 0.04
 C41-C23 \\sim C41A-C23A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
O9 \\sim O37 \\sim C53 \\sim C105 \\sim C211 \\sim C213: within 3A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 3A
O2 \\sim O2A \\sim O20 \\sim C1A \\sim C1B \\sim C83 \\sim C101 \\sim C103
\\sim C207 \\sim C223: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
P7 \\sim F11 \\sim F21 \\sim F23 \\sim F39 \\sim F41 \\sim F47 \\sim P7A \\sim
F11A \\sim F21A \\sim F23A \\sim F39A \\sim F41A \\sim F47A: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O15 \\sim O15A \\sim O22 \\sim C1C \\sim C13 \\sim C13A \\sim C43 \\sim C195
\\sim C209 \\sim C224: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O16 \\sim O38 \\sim C51 \\sim C51A \\sim C159 \\sim C179 \\sim C197 \\sim C225:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O7 \\sim O7A \\sim O42 \\sim O42A \\sim C23 \\sim C23A \\sim C41 \\sim C41A
\\sim C93 \\sim C199: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02 within 2A
O19 \\sim O19A \\sim O35 \\sim C1D \\sim C1E \\sim C27 \\sim C27A \\sim C107
\\sim C215 \\sim C217 \\sim C226: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
O31 \\sim O33 \\sim C181 \\sim C201 \\sim C203 \\sim C205 \\sim O31A \\sim O33A
\\sim C1F \\sim C1G \\sim C1H \\sim C227: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
O13 \\sim O25 \\sim C3 \\sim C25 \\sim C95 \\sim C173 \\sim O13A \\sim O25A
\\sim C3A \\sim C25A \\sim C95A \\sim C228: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
O5 \\sim O41 \\sim C55 \\sim C109 \\sim C219 \\sim C221 \\sim O5A \\sim O41A
\\sim C1I \\sim C1J \\sim C55A \\sim C229: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
Uanis(C213) \\sim Ueq, Uanis(C105) \\sim Ueq, Uanis(O9) \\sim Ueq, Uanis(C53)
\\sim Ueq, Uanis(O37) \\sim Ueq, Uanis(C211) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
4. Others
 Sof(O2A)=Sof(C1A)=Sof(HH)=Sof(HI)=Sof(C1B)=Sof(HJ)=Sof(HK)=Sof(HN)=Sof(HO)=
 Sof(C223)=Sof(HV)=Sof(HW)=1-FVAR(1)
 Sof(O2)=Sof(HL)=Sof(HM)=Sof(C101)=Sof(HP)=Sof(HQ)=Sof(C103)=Sof(HR)=Sof(HS)=
 Sof(C207)=Sof(HT)=Sof(HU)=FVAR(1)
 Sof(P7A)=Sof(F11A)=Sof(F21A)=Sof(F23A)=Sof(F39A)=Sof(F41A)=Sof(F47A)=1-FVAR(2)
 Sof(P7)=Sof(F11)=Sof(F21)=Sof(F23)=Sof(F39)=Sof(F41)=Sof(F47)=FVAR(2)
 Sof(O15A)=Sof(C1C)=Sof(H94)=Sof(H95)=Sof(C13A)=Sof(H98)=Sof(H99)=Sof(H102)=
 Sof(H103)=Sof(C224)=Sof(H108)=Sof(H109)=1-FVAR(3)
 Sof(O15)=Sof(C13)=Sof(H96)=Sof(H97)=Sof(H100)=Sof(H101)=Sof(C195)=Sof(H104)=
 Sof(H105)=Sof(C209)=Sof(H106)=Sof(H107)=FVAR(3)
 Sof(C51A)=Sof(H112)=Sof(H113)=Sof(H116)=Sof(H117)=Sof(H120)=Sof(H121)=
 Sof(C225)=Sof(H124)=Sof(H125)=1-FVAR(4)
 Sof(C51)=Sof(H110)=Sof(H111)=Sof(H114)=Sof(H115)=Sof(H118)=Sof(H119)=
 Sof(C197)=Sof(H122)=Sof(H123)=FVAR(4)
 Sof(O7A)=Sof(O42A)=Sof(C23A)=Sof(H32)=Sof(H33)=Sof(C41A)=Sof(H36)=Sof(H37)=
 Sof(H40)=Sof(H41)=Sof(H44)=Sof(H45)=1-FVAR(5)
 Sof(O7)=Sof(O42)=Sof(C23)=Sof(H30)=Sof(H31)=Sof(C41)=Sof(H34)=Sof(H35)=
 Sof(H38)=Sof(H39)=Sof(H42)=Sof(H43)=FVAR(5)
 Sof(O19A)=Sof(C1D)=Sof(H128)=Sof(H129)=Sof(C1E)=Sof(H130)=Sof(H131)=Sof(C27A)=
 Sof(H134)=Sof(H135)=Sof(C226)=Sof(H142)=Sof(H143)=1-FVAR(6)
 Sof(O19)=Sof(C27)=Sof(H132)=Sof(H133)=Sof(C107)=Sof(H136)=Sof(H137)=Sof(C215)=
 Sof(H138)=Sof(H139)=Sof(C217)=Sof(H140)=Sof(H141)=FVAR(6)
 Sof(O31A)=Sof(O33A)=Sof(C1F)=Sof(H184)=Sof(H185)=Sof(C1G)=Sof(H186)=Sof(H187)=
 Sof(C1H)=Sof(H188)=Sof(H189)=Sof(C227)=Sof(H190)=Sof(H191)=1-FVAR(7)
 Sof(O31)=Sof(O33)=Sof(C181)=Sof(H176)=Sof(H177)=Sof(C201)=Sof(H178)=Sof(H179)=
 Sof(C203)=Sof(H180)=Sof(H181)=Sof(C205)=Sof(H182)=Sof(H183)=FVAR(7)
 Sof(O13A)=Sof(O25A)=Sof(C3A)=Sof(H86)=Sof(H87)=Sof(C25A)=Sof(H88)=Sof(H89)=
 Sof(C95A)=Sof(H90)=Sof(H91)=Sof(C228)=Sof(H92)=Sof(H93)=1-FVAR(8)
 Sof(O13)=Sof(O25)=Sof(C3)=Sof(H78)=Sof(H79)=Sof(C25)=Sof(H80)=Sof(H81)=
 Sof(C95)=Sof(H82)=Sof(H83)=Sof(C173)=Sof(H84)=Sof(H85)=FVAR(8)
 Sof(O5A)=Sof(O41A)=Sof(C1I)=Sof(H14)=Sof(H15)=Sof(C1J)=Sof(H16)=Sof(H17)=
 Sof(C55A)=Sof(H18)=Sof(H19)=Sof(C229)=Sof(H20)=Sof(H21)=1-FVAR(9)
 Sof(O5)=Sof(O41)=Sof(C55)=Sof(H6)=Sof(H7)=Sof(C109)=Sof(H8)=Sof(H9)=Sof(C219)=
 Sof(H10)=Sof(H11)=Sof(C221)=Sof(H12)=Sof(H13)=FVAR(9)
5.a Riding coordinates:
 O17(H126,H127), O39(H200,H201)
5.b Secondary CH2 refined with riding coordinates:
 C9(H,HA), C73(HB,HC), C143(HD,HE), C147(HF,HG), C1A(HH,HI), C1B(HJ,HK),
 C83(HL,HM), C83(HN,HO), C101(HP,HQ), C103(HR,HS), C207(HT,HU), C223(HV,HW),
 C11(HX,HY), C47(HZ,H1), C183(H2,H3), C185(H4,H5), C55(H6,H7), C109(H8,H9),
 C219(H10,H11), C221(H12,H13), C1I(H14,H15), C1J(H16,H17), C55A(H18,H19),
 C229(H20,H21), C17(H22,H23), C39(H24,H25), C75(H26,H27), C155(H28,H29),
 C23(H30,H31), C23A(H32,H33), C41(H34,H35), C41A(H36,H37), C93(H38,H39),
 C93(H40,H41), C199(H42,H43), C199(H44,H45), C19(H46,H47), C77(H48,H49),
 C139(H50,H51), C149(H52,H53), C53(H54,H55), C105(H56,H57), C211(H58,H59),
 C213(H60,H61), C81(H62,H63), C85(H64,H65), C89(H66,H67), C165(H68,H69),
 C37(H70,H71), C141(H72,H73), C151(H74,H75), C153(H76,H77), C3(H78,H79),
 C25(H80,H81), C95(H82,H83), C173(H84,H85), C3A(H86,H87), C25A(H88,H89),
 C95A(H90,H91), C228(H92,H93), C1C(H94,H95), C13(H96,H97), C13A(H98,H99),
 C43(H100,H101), C43(H102,H103), C195(H104,H105), C209(H106,H107), C224(H108,
 H109), C51(H110,H111), C51A(H112,H113), C159(H114,H115), C159(H116,H117),
 C179(H118,H119), C179(H120,H121), C197(H122,H123), C225(H124,H125), C1D(H128,
 H129), C1E(H130,H131), C27(H132,H133), C27A(H134,H135), C107(H136,H137),
 C215(H138,H139), C217(H140,H141), C226(H142,H143), C45(H144,H145), C97(H146,
 H147), C99(H148,H149), C189(H150,H151), C21(H152,H153), C79(H154,H155),
 C163(H156,H157), C167(H158,H159), C49(H160,H161), C187(H162,H163), C191(H164,
 H165), C193(H166,H167), C87(H168,H169), C161(H170,H171), C169(H172,H173),
 C171(H174,H175), C181(H176,H177), C201(H178,H179), C203(H180,H181), C205(H182,
 H183), C1F(H184,H185), C1G(H186,H187), C1H(H188,H189), C227(H190,H191),
 C5(H192,H193), C157(H194,H195), C175(H196,H197), C177(H198,H199), C31(H211,
 H212), C35(H217,H218), C61(H228,H229), C78(H241,H242), C123(H260,H261),
 C125(H262,H263), C156(H284,H285), C174(H294,H295)
5.c Aromatic/amide H refined with riding coordinates:
 C6(H205), C7(H206), C15(H207), C24(H208), C28(H209), C29(H210), C32(H213),
 C38(H219), C50(H220), C52(H221), C54(H222), C58(H226), C59(H227), C62(H230),
 C65(H234), C67(H235), C68(H236), C69(H237), C71(H238), C72(H239), C74(H240),
 C80(H243), C88(H244), C94(H245), C96(H246), C100(H247), C104(H248), C108(H252),
  C111(H253), C113(H254), C115(H255), C116(H256), C117(H257), C118(H258),
 C119(H259), C127(H264), C129(H265), C131(H266), C132(H267), C137(H274),
 C138(H275), C144(H279), C150(H283), C158(H286), C162(H287), C166(H288),
 C170(H292), C172(H293), C176(H296), C178(H297), C180(H298), C186(H302),
 C190(H306), C192(H307), C194(H308), C196(H309), C198(H310), C200(H311),
 C204(H312), C208(H316), C214(H323), C216(H324), C218(H325), C222(H329)
5.d Idealised Me refined as rotating group:
 C2(H202,H203,H204), C33(H214,H215,H216), C57(H223,H224,H225), C63(H231,H232,
 H233), C106(H249,H250,H251), C133(H268,H269,H270), C135(H271,H272,H273),
 C142(H276,H277,H278), C146(H280,H281,H282), C168(H289,H290,H291), C182(H299,
 H300,H301), C188(H303,H304,H305), C206(H313,H314,H315), C210(H317,H318,H319),
 C212(H320,H321,H322), C220(H326,H327,H328), C91(H330,H331,H332)
;
_shelx_res_checksum              28669
_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 2.168
_oxdiff_exptl_absorpt_empirical_full_min 0.479