Porous shape-persistent rylene imine cages with tunable optoelectronic properties and delayed fluorescence
Huang, Hsin-Hua; Song, Kyung Seob; Prescimone, Alessandro; Aster, Alexander; Cohen, Gabriel; Mannancherry, Rajesh; Vauthey, Eric; Coskun, Ali; Šolomek, Tomáš; Chemical Science 12 (2021) 5275–5285; doi:10.1039/D1SC00347J

data_1560985
_publ_section_title
;
 Porous shape-persistent rylene imine cages with tunable optoelectronic
 properties and delayed fluorescence
;
_journal_issue                   14
_journal_name_full               'Chemical Science'
_journal_page_first              5275
_journal_page_last               5285
_journal_paper_doi               10.1039/D1SC00347J
_journal_volume                  12
_journal_year                    2021
_chemical_absolute_configuration ad
_chemical_formula_moiety
'C84 H78 N12 O12, 5(C6 H5 N O2), C0.6 H1.5 O0.3, 0.9(C H4 O)'
_chemical_formula_sum            'C115.5 H108.1 N17 O23.2'
_chemical_formula_weight         2105.48
_space_group_crystal_system      monoclinic
_space_group_IT_number           5
_space_group_name_Hall           'C 2y'
_space_group_name_H-M_alt        'C 1 2 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2665qb
_audit_creation_date             2019-08-14
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-09-13 deposited with the CCDC.	2021-02-11 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 102.403(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   31.8864(19)
_cell_length_b                   17.2148(10)
_cell_length_c                   20.9689(12)
_cell_measurement_reflns_used    9923
_cell_measurement_temperature    130
_cell_measurement_theta_max      70.319
_cell_measurement_theta_min      3.918
_cell_volume                     11241.6(11)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_collection       'Apex2 (Bruker AXS, 2006)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      130
_diffrn_measured_fraction_theta_full 0.996
_diffrn_measured_fraction_theta_max 0.974
_diffrn_measurement_device       Area
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f & \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0374
_diffrn_reflns_av_unetI/netI     0.0307
_diffrn_reflns_Laue_measured_fraction_full 0.996
_diffrn_reflns_Laue_measured_fraction_max 0.974
_diffrn_reflns_limit_h_max       38
_diffrn_reflns_limit_h_min       -37
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            74017
_diffrn_reflns_point_group_measured_fraction_full 0.927
_diffrn_reflns_point_group_measured_fraction_max 0.897
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         70.336
_diffrn_reflns_theta_min         2.838
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.728
_exptl_absorpt_correction_T_max  0.7533
_exptl_absorpt_correction_T_min  0.6898
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0756 before and 0.0462 after correction.
The Ratio of minimum to maximum transmission is 0.9157.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.244
_exptl_crystal_description       needle
_exptl_crystal_F_000             4423
_exptl_crystal_recrystallization_method
'The material was recrystallised from a mixture of methanol and nitro-benzene  by solvent layering'
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.05
_refine_diff_density_max         1.318
_refine_diff_density_min         -0.488
_refine_diff_density_rms         0.096
_refine_ls_abs_structure_details
;
 Flack x determined using 7307 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.14(5)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.053
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1472
_refine_ls_number_reflns         19234
_refine_ls_number_restraints     78
_refine_ls_restrained_S_all      1.054
_refine_ls_R_factor_all          0.0746
_refine_ls_R_factor_gt           0.0713
_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^)+(0.1665P)^2^+7.3061P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2088
_refine_ls_wR_factor_ref         0.2145
_reflns_Friedel_coverage         0.778
_reflns_Friedel_fraction_full    0.852
_reflns_Friedel_fraction_max     0.814
_reflns_number_gt                18073
_reflns_number_total             19234
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc00347j2.cif
_cod_data_source_block           hh_plcycage99_130k_0m
_cod_depositor_comments
'Adding full bibliography for 1560984--1560985.cif.'
_cod_original_formula_sum        'C115.50 H108.10 N17 O23.20'
_cod_database_code               1560985
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.965
_shelx_estimated_absorpt_t_min   0.839
_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, All O(H) groups
2. Restrained distances
 C120-C115 \\sim C116-C115 \\sim C116-C117 \\sim C118-C117 \\sim C118-C119
\\sim C120-C119
 with sigma of 0.02
 C95-C94 \\sim C95-C96 \\sim C93-C94 \\sim C92-C93 \\sim C91-C92 \\sim C91-C96
 with sigma of 0.02
 C126-C125 \\sim C125-C124 \\sim C123-C124 \\sim C123-C122 \\sim C121-C122
\\sim C126-C121
 with sigma of 0.02
 C102-C97 \\sim C102-C101 \\sim C100-C99 \\sim C98-C97 \\sim C98-C99 \\sim
C100-C101 \\sim C100-C99
 with sigma of 0.02
3. Restrained planarity
 C120, C115, C116, C117, C118, C119, N18
 with sigma of 0.1
 C93, C92, C91, C96, C95, C94, N14, O16, O15
 with sigma of 0.1
 C121, C126, C125, C124, C123, C122
 with sigma of 0.1
 N15, C97, C98, C99, C100, C101, C102
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
: with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(O15) = Uanis(O16) = Uanis(N14)
Uanis(C128) = Uanis(O29)
Uanis(C97) = Uanis(C98) = Uanis(C99) = Uanis(C100) = Uanis(C101) = Uanis(C102)
Uanis(C92) = Uanis(C93) = Uanis(C94) = Uanis(C95) = Uanis(C96) = Uanis(C91)
Uanis(O17) = Uanis(N15) = Uanis(O18)
Uanis(O16) = Uanis(N14) = Uanis(O15)
5. Others
 Fixed Sof: C122(0.5) H122(0.5) C124(0.5) H124(0.5) C121(0.5) C123(0.5)
 H123(0.5) N19(0.5) C125(0.5) H125(0.5) C126(0.5) H126(0.5) O22(0.5) O21(0.5)
 C93(0.5) H93(0.5) C95(0.5) H95(0.5) C92(0.5) H92(0.5) C91(0.5) O16(0.5)
 C94(0.5) H94(0.5) N14(0.5) C96(0.5) H96(0.5) O15(0.5) O28(0.3) H28(0.6)
 C129(0.6) H12C(0.3) H12D(0.3) H12E(0.3) C117(0.5) H117(0.5) C116(0.5)
 H116(0.5) C118(0.5) H118(0.5) N15(0.5) C115(0.5) O17(0.5) O18(0.5) C120(0.5)
 H120(0.5) C119(0.5) H119(0.5) O24(0.5) N18(0.5) O23(0.5) C97(0.5) C98(0.5)
 H98(0.5) C102(0.5) H102(0.5) C99(0.5) H99(0.5) C101(0.5) H101(0.5) C100(0.5)
 H100(0.5) O27(0.5) H27A(0.5) C127(0.5) H12F(0.5) H12G(0.5) H12H(0.5) O29(0.4)
 H29(0.4) C128(0.4) H12I(0.4) H12J(0.4) H12K(0.4)
6.a Riding coordinates:
 O28(H28), C129(H12C,H12D,H12E), O29(H29), C128(H12I,H12J,H12K)
6.b Ternary CH refined with riding coordinates:
 C57(H57), C27(H27), C42(H42), C11(H11), C58(H58), C41(H41), C26(H26),
 C10(H10), C79(H79), C63(H63), C80(H80), C64(H64)
6.c Secondary CH2 refined with riding coordinates:
 C59(H59A,H59B), C62(H62A,H62B), C29(H29A,H29B), C28(H28A,H28B), C14(H14A,
 H14B), C61(H61A,H61B), C30(H30A,H30B), C43(H43A,H43B), C44(H44A,H44B),
 C15(H15A,H15B), C45(H45A,H45B), C13(H13A,H13B), C12(H12A,H12B), C60(H60A,H60B),
  C31(H31A,H31B), C81(H81A,H81B), C46(H46A,H46B), C84(H84A,H84B), C66(H66A,
 H66B), C83(H83A,H83B), C65(H65A,H65B), C67(H67A,H67B), C82(H82A,H82B),
 C68(H68A,H68B)
6.d Aromatic/amide H refined with riding coordinates:
 C5(H5), C34(H34), C49(H49), C53(H53), C39(H39), C36(H36), C40(H40), C1(H1),
 C32(H32), C8(H8), C37(H37), C3(H3), C20(H20), C6(H6), C9(H9), C25(H25),
 C110(H110), C114(H114), C112(H112), C113(H113), C78(H78), C73(H73), C111(H111),
  C104(H104), C105(H105), C122(H122), C86(H86), C106(H106), C88(H88),
 C108(H108), C90(H90), C124(H124), C123(H123), C125(H125), C89(H89), C126(H126),
  C107(H107), C87(H87), C93(H93), C95(H95), C92(H92), C94(H94), C96(H96),
 C117(H117), C116(H116), C118(H118), C120(H120), C119(H119), C98(H98),
 C102(H102), C99(H99), C101(H101), C100(H100)
6.e Idealised Me refined as rotating group:
 C127(H12F,H12G,H12H)
6.f Idealised tetrahedral OH refined as rotating group:
 O27(H27A)
;
_shelx_res_checksum              56310
_shelx_hkl_checksum              74586
_olex2_date_sample_data_collection 2019-08-12
_olex2_date_sample_submission    2019-07-08
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a mylar loop in perfluoroether oil'
_olex2_submission_original_sample_id HH_PlcyCage99_130K
_olex2_submission_special_instructions 'No special instructions were received'