Structure-enabled long-lived charge separation in single crystals of an asymmetric donor-acceptor perylenediimide cyclophane.
Williams, Malik L.; Coleman, Adam F.; Peinkofer, Kathryn R.; Young, Ryan M.; Wasielewski, Michael R.; Chemical science 15 (2024) 11472–11479; doi:10.1039/d4sc03359k

data_1571960
_publ_section_title
;
 Structure-enabled long-lived charge separation in single crystals of an
 asymmetric donor-acceptor perylenediimide cyclophane.
;
_journal_issue                   29
_journal_name_full               'Chemical science'
_journal_page_first              11472
_journal_page_last               11479
_journal_paper_doi               10.1039/d4sc03359k
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C112 H91 N6 O12, 3(C7 H8)'
_chemical_formula_sum            'C133 H115 N6 O12'
_chemical_formula_weight         1989.30
_chemical_name_systematic        1AFC-An
_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   geom
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2jmx47
_audit_creation_date             2024-03-24
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-03-24 deposited with the CCDC.	2024-06-20 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.666(4)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.4426(12)
_cell_length_b                   20.9039(10)
_cell_length_c                   30.0536(10)
_cell_measurement_reflns_used    9107
_cell_measurement_temperature    100.01(10)
_cell_measurement_theta_max      61.1820
_cell_measurement_theta_min      3.3480
_cell_volume                     14004.0(11)
_computing_cell_refinement       'CrysAlisPro 1.171.41.76a (Rigaku OD, 2020)'
_computing_data_collection       'CrysAlisPro 1.171.41.76a (Rigaku OD, 2020)'
_computing_data_reduction        'CrysAlisPro 1.171.41.76a (Rigaku OD, 2020)'
_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 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.01(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_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   -150.00 -63.00   0.50   45.00    --  -88.69-142.00 -55.00  174
  2  \w    -97.00 -72.00   0.50   45.00    --  -88.69 142.00   1.00   50
  3  \w   -114.00 -17.00   0.50   45.00    --  -88.69 128.00-169.00  194
  4  \w     49.00  74.00   0.50   45.00    --   90.57-142.00 -55.00   50
  5  \w     84.00 113.00   0.50   45.00    --   90.57-128.00 115.00   58
  6  \w     66.00  92.00   0.50   45.00    --   90.57 142.00   1.00   52
  7  \w    -71.00  10.00   0.50   20.00    --    0.94 -19.00 150.00  162
  8  \w    -17.00  34.00   0.50   20.00    --    0.94 -99.00  30.00  102
  9  \w    -22.00  14.00   0.50   20.00    --    0.94 -99.00-180.00   72
 10  \w    -41.00 -15.00   0.50   45.00    --  -88.69  37.00  60.00   52
 11  \w    -55.00 -18.00   0.50   45.00    --  -88.69   0.00  90.00   74
 12  \w    -76.00 -21.00   0.50   45.00    --  -88.69   0.00-150.00  110
 13  \w    -66.00 -37.00   0.50   45.00    --  -88.69  57.00 150.00   58
 14  \w    -68.00 -18.00   0.50   45.00    --  -88.69  57.00-150.00  100
 15  \w    -42.00 -15.00   0.50   45.00    --  -88.69  37.00 -60.00   54
 16  \w    -68.00 -43.00   0.50   45.00    --  -88.69  57.00-180.00   50
 17  \w   -102.00 -16.00   0.50   45.00    --  -88.69  77.00   0.00  172
 18  \w     78.00 138.00   0.50   45.00    --   90.57  57.00 -60.00  120
 19  \w     25.00 107.00   0.50   45.00    --   90.57-125.00  60.00  164
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0240417000
_diffrn_orient_matrix_UB_12      -0.0659153000
_diffrn_orient_matrix_UB_13      -0.0122065000
_diffrn_orient_matrix_UB_21      0.0526561000
_diffrn_orient_matrix_UB_22      0.0326757000
_diffrn_orient_matrix_UB_23      -0.0196870000
_diffrn_orient_matrix_UB_31      0.0377985000
_diffrn_orient_matrix_UB_32      -0.0035489000
_diffrn_orient_matrix_UB_33      0.0461329000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0460
_diffrn_reflns_av_unetI/netI     0.0390
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -23
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -27
_diffrn_reflns_number            71366
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        55.095
_diffrn_reflns_theta_max         55.095
_diffrn_reflns_theta_min         3.358
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.478
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.70372
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.76a (Rigaku Oxford Diffraction, 2020)
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    0.944
_exptl_crystal_description       plate
_exptl_crystal_F_000             4204
_exptl_crystal_preparation       'Grown in a 100:1 An:1AFC104'
_exptl_crystal_recrystallization_method Toluene:Methanol
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.222
_exptl_crystal_size_min          0.126
_refine_diff_density_max         0.802
_refine_diff_density_min         -0.408
_refine_diff_density_rms         0.070
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.302
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1440
_refine_ls_number_reflns         17628
_refine_ls_number_restraints     1633
_refine_ls_restrained_S_all      1.301
_refine_ls_R_factor_all          0.1341
_refine_ls_R_factor_gt           0.1055
_refine_ls_shift/su_max          3.741
_refine_ls_shift/su_mean         0.034
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3262
_refine_ls_wR_factor_ref         0.3502
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11173
_reflns_number_total             17628
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc03359k2.cif
_cod_data_source_block           1afc104-an_auto
_cod_depositor_comments          'Adding full bibliography for 1571960.cif.'
_cod_database_code               1571960
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C126H108N6O12
_shelx_estimated_absorpt_t_max   0.942
_shelx_estimated_absorpt_t_min   0.870
_reflns_odcompleteness_completeness 99.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     55.03
_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
 C34-C02Y = C34-C117 = C34-C123 = C34-C174
 1.54 with sigma of 0.02
 C135-C03B = C135-C111 = C135-C153 = C135-C158
 1.54 with sigma of 0.02
 C55-C032 = C55-C126 = C55-C162 = C55-C148
 1.54 with sigma of 0.02
 C11-C12
 1.51 with sigma of 0.02
 C12-C13 = C12-C17 = C14-C15
 1.39 with sigma of 0.02
 C13-C14 = C15-C16 = C16-C17
 1.38 with sigma of 0.02
 C18-C19
 1.51 with sigma of 0.02
 C19-C1J = C19-C1N = C1K-C1L
 1.39 with sigma of 0.02
 C1J-C1K = C1L-C1M = C1M-C1N
 1.38 with sigma of 0.02
 C11-C13 = C11-C17
 2.52 with sigma of 0.04
 C12-C14
 2.42 with sigma of 0.04
 C12-C16
 2.41 with sigma of 0.04
 C13-C15
 2.39 with sigma of 0.04
 C14-C16 = C15-C17
 2.4 with sigma of 0.04
 C18-C1J = C18-C1N
 2.52 with sigma of 0.04
 C19-C1K
 2.42 with sigma of 0.04
 C19-C1M
 2.41 with sigma of 0.04
 C1J-C1L
 2.39 with sigma of 0.04
 C1K-C1M = C1L-C1N
 2.4 with sigma of 0.04
 C12-C13 \\sim C13-C14 \\sim C14-C15 \\sim C15-C16 \\sim C16-C17 \\sim C17-C12
 with sigma of 0.02
 C12-C16 \\sim C12-C14 \\sim C17-C15 \\sim C13-C17 \\sim C14-C16 \\sim C13-C15
 with sigma of 0.04
 C11-C17 \\sim C11-C13
 with sigma of 0.04
 C19-C1J \\sim C1J-C1K \\sim C1K-C1L \\sim C1L-C1M \\sim C1M-C1N \\sim C1N-C19
 with sigma of 0.02
 C19-C1M \\sim C19-C1K \\sim C1N-C1L \\sim C1J-C1N \\sim C1K-C1M \\sim C1J-C1L
 with sigma of 0.04
 C18-C1N \\sim C18-C1J
 with sigma of 0.04
 O00G-C029 \\sim O1-C029
 with sigma of 0.02
 O00G-C3 \\sim O1-C3A
 with sigma of 0.02
 C3-C22 \\sim C3A-C22A
 with sigma of 0.02
 C3-C10 \\sim C3A-C10A
 with sigma of 0.02
 C22-C21 \\sim C22A-C21A
 with sigma of 0.02
 C10-C20 \\sim C10A-C20A
 with sigma of 0.02
 C23-C21 \\sim C23A-C21A
 with sigma of 0.02
 C23-C20 \\sim C23A-C20A
 with sigma of 0.02
 C23-C24 \\sim C23A-C24A
 with sigma of 0.02
 C24-C27 \\sim C24A-C27A
 with sigma of 0.02
 C24-C26 \\sim C24A-C26A
 with sigma of 0.02
 C24-C25 \\sim C24A-C25A
 with sigma of 0.02
 O00G-C22 \\sim O1-C22A
 with sigma of 0.04
 O00G-C10 \\sim O1-C10A
 with sigma of 0.04
 C029-C3 \\sim C029-C3A
 with sigma of 0.04
 C3-C21 \\sim C3A-C21A
 with sigma of 0.04
 C3-C20 \\sim C3A-C20A
 with sigma of 0.04
 C22-C10 \\sim C22A-C10A
 with sigma of 0.04
 C22-C23 \\sim C22A-C23A
 with sigma of 0.04
 C10-C23 \\sim C10A-C23A
 with sigma of 0.04
 C23-C27 \\sim C23A-C27A
 with sigma of 0.04
 C23-C26 \\sim C23A-C26A
 with sigma of 0.04
 C23-C25 \\sim C23A-C25A
 with sigma of 0.04
 C21-C20 \\sim C21A-C20A
 with sigma of 0.04
 C21-C24 \\sim C21A-C24A
 with sigma of 0.04
 C20-C24 \\sim C20A-C24A
 with sigma of 0.04
 C27-C26 \\sim C27A-C26A
 with sigma of 0.04
 C27-C25 \\sim C27A-C25A
 with sigma of 0.04
 C26-C25 \\sim C26A-C25A
 with sigma of 0.04
3. Restrained planarity
 C11, C12, C13, C14, C15, C16, C17
 with sigma of 0.1
 C18, C19, C1J, C1K, C1L, C1M, C1N
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
C11 \\sim C12 \\sim C13 \\sim C14 \\sim C15 \\sim C16 \\sim C17: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
C18 \\sim C19 \\sim C1J \\sim C1K \\sim C1L \\sim C1M \\sim C1N: within 2A with
sigma of 0.04 and sigma for terminal atoms of 0.08 within 2A
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C11, C12, C13, C14, C15, C16, C17
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C18, C19, C1J, C1K, C1L, C1M, C1N
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(O1)=1-FVAR(1)
 Sof(O00G)=FVAR(1)
 Fixed Sof: C3(0.5) C22(0.5) H22(0.5) C10(0.5) H10(0.5) C23(0.5) C21(0.5)
 H21(0.5) C20(0.5) H20(0.5) C24(0.5) C27(0.5) H27a(0.5) H27b(0.5) H27c(0.5)
 C26(0.5) C25(0.5) H25a(0.5) H25b(0.5) H25c(0.5) C3A(0.5) C22A(0.5) H22A(0.5)
 C10A(0.5) H10A(0.5) C23A(0.5) C21A(0.5) H21A(0.5) C20A(0.5) H20A(0.5)
 C24A(0.5) C27A(0.5) H27d(0.5) H27e(0.5) H27f(0.5) C25A(0.5) H25d(0.5)
 H25e(0.5) H25f(0.5) C26A(0.5)
7.a Secondary CH2 refined with riding coordinates:
 C01P(H01b,H01d), C01T(H01e,H01f), C023(H02a,H02b), C027(H02c,H02d), C02C(H02f,
 H02g), C02E(H02i,H02j), C02F(H02k,H02l), C02G(H02m,H02n), C02K(H02p,H02q),
 C02M(H02s,H02t), C02P(H02u,H02v), C02X(H02z,H)
7.b Aromatic/amide H refined with riding coordinates:
 C016(H016), C01A(H01A), C01C(H01C), C01G(H01G), C01H(H01H), C01I(H01I),
 C01J(H01J), C01Q(H01Q), C01W(H01W), C01X(H01X), C01Y(H01Y), C01Z(H01Z),
 C020(H020), C022(H022), C024(H024), C028(H028), C02B(H02e), C02D(H02h),
 C02J(H02o), C02L(H02r), C02R(H02w), C02N(H02x), C034(H034), C039(H039),
 C02T(H02y), C02Q(H02), C02I(H1), C02O(H2), C030(H030), C031(H031), C4(H4),
 C9(H9), C7(H7), C5(H5), C1(H1a), C13(H13), C14(H14), C15(H15), C16(H16),
 C17(H17), C1J(H1J), C1K(H1K), C1L(H1L), C1M(H1M), C1N(H1N), C22(H22), C10(H10),
  C21(H21), C20(H20), C22A(H22A), C10A(H10A), C21A(H21A), C20A(H20A)
7.c Fitted hexagon refined as free rotating group:
 C02R(C02H,C02N,C034,C03B,C039), C02Y(C02Q,C02I,C02A,C02O,C030), C6(C4,C9,C7,
 C5,C1)
7.d Idealised Me refined as rotating group:
 C111(H11a,H11b,H11c), C117(H11d,H11e,H11f), C123(H12a,H12b,H12c), C126(H12d,
 H12e,H12f), C153(H15a,H15b,H15c), C162(H16a,H16b,H16c), C174(H17a,H17b,H17c),
 C148(H14a,H14b,H14c), C158(H15d,H15e,H15f), C8(H8a,H8b,H8c), C11(H11g,H11h,
 H11i), C18(H18a,H18b,H18c), C27(H27a,H27b,H27c), C25(H25a,H25b,H25c),
 C27A(H27d,H27e,H27f), C25A(H25d,H25e,H25f)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              55235
_shelx_fab_checksum              79925
_olex2_exptl_crystal_mounting_method 'Moutned using paraffin oil'
_olex2_submission_original_sample_id 1AFC104-An
_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 1.544
_oxdiff_exptl_absorpt_empirical_full_min 0.568