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_1560984
_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, 4.8(C7 H5 O2), C0.5 H3.5 O0.5, 0.9(C H4 O)'
_chemical_formula_sum            'C119 H109.1 N12 O23'
_chemical_formula_weight         2075.28
_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.cc2665p9
_audit_creation_date             2019-08-20
_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                 102.3150(10)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   31.9058(6)
_cell_length_b                   17.2344(3)
_cell_length_c                   20.9913(4)
_cell_measurement_reflns_used    99325
_cell_measurement_temperature    130
_cell_measurement_theta_max      57.45
_cell_measurement_theta_min      2.76
_cell_volume                     11277.0(4)
_computing_cell_refinement
;
X-Area Recipe 1.33.0.0 (STOE, 2015)
;
_computing_data_collection
;
X-Area Pilatus3_SV 1.31.153.0 (STOE, 2018)
;
_computing_data_reduction
;
X-Area Integrate 1.74.2.0 (STOE, 2018)
X-Area LANA 1.75.3.0 (STOE, 2018)
;
_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_detector                 Pilatus300K
_diffrn_detector_area_resol_mean 5.81
_diffrn_detector_type            'DECTRIS PILATUS 300K'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.969
_diffrn_measurement_details      ' 4172 frames, detector distance = 60 mm'
_diffrn_measurement_device       'Eulerian 4-circle diffractometer'
_diffrn_measurement_device_type  'Stoe StadiVari'
_diffrn_measurement_method       'rotation method, \w scans'
_diffrn_radiation_collimation    '1.2 0.6 mm diameter'
_diffrn_radiation_monochromator  'Graded multilayer mirror'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34143
_diffrn_reflns_av_R_equivalents  0.0365
_diffrn_reflns_av_unetI/netI     0.0292
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.969
_diffrn_reflns_limit_h_max       38
_diffrn_reflns_limit_h_min       -38
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            60720
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.934
_diffrn_reflns_theta_full        53.597
_diffrn_reflns_theta_max         57.230
_diffrn_reflns_theta_min         3.004
_diffrn_source                   'Metaljet D2'
_diffrn_source_current           3.570
_diffrn_source_power             0.250
_diffrn_source_voltage           70
_exptl_absorpt_coefficient_mu    0.451
_exptl_absorpt_correction_T_max  0.9954
_exptl_absorpt_correction_T_min  0.9837
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
STOE X-Red32, absorption correction by Gaussian integration, analogous to
P. Coppens, "The Evaluation of Absorption and Extinction in Single-Crystal
Structure Analysis", published in: F. R. Ahmed (Editor), "Crystallographic
Computing", Munksgaard, Copenhagen (1970), 255 - 270.
Afterwards scaling of reflection intensities was performed within STOE LANA.
J. Koziskova, F. Hahn, J. Richter, J. Kozisek, "Comparison of different
absorption corrections on the model structure of tetrakis(\m~2~-acetato)-
diaqua-di-copper(II)", Acta Chimica Slovaca, vol. 9, no. 2, 2016, pp. 136 - 140.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.222
_exptl_crystal_description       block
_exptl_crystal_F_000             4364
_exptl_crystal_recrystallization_method 'Vapour deposition'
_exptl_crystal_size_max          0.22
_exptl_crystal_size_mid          0.173
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.297
_refine_diff_density_min         -0.415
_refine_diff_density_rms         0.105
_refine_ls_abs_structure_details
;
 Flack x determined using 8008 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.02(3)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.083
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1395
_refine_ls_number_reflns         21729
_refine_ls_number_restraints     98
_refine_ls_restrained_S_all      1.087
_refine_ls_R_factor_all          0.0984
_refine_ls_R_factor_gt           0.0879
_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^)+(0.1679P)^2^+22.1789P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2449
_refine_ls_wR_factor_ref         0.2617
_reflns_Friedel_coverage         0.862
_reflns_Friedel_fraction_full    0.968
_reflns_Friedel_fraction_max     0.895
_reflns_number_gt                19674
_reflns_number_total             21729
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d1sc00347j2.cif
_cod_data_source_block           hh_plcycage138rr_130k
_cod_depositor_comments
'Adding full bibliography for 1560984--1560985.cif.'
_cod_original_formula_sum        'C119 H109.10 N12 O23'
_cod_database_code               1560984
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.956
_shelx_estimated_absorpt_t_min   0.907
_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
 O136-H136
 0.82 with sigma of 0.02
 O27-H27A
 0.82 with sigma of 0.02
 O1A-H1A
 0.82 with sigma of 0.02
 C97-C96 = C96-C95 = C95-C94 = C94-C93 = C98-C93 = C98-C97 = C93-C92
 1.38 with sigma of 0.002
 C103-C102 \\sim C103-C104 \\sim C105-C104 \\sim C105-C100 \\sim C100-C101
\\sim C102-C101
 with sigma of 0.02
 C94-C95 \\sim C96-C95 \\sim C97-C96 \\sim C93-C94 \\sim C98-C93 \\sim C98-C97
 with sigma of 0.02
 C88-C89 \\sim C88-C87 \\sim C87-C86 \\sim C91-C86 \\sim C90-C91 \\sim C90-C89
 with sigma of 0.02
 C107-C108 \\sim C111-C110 \\sim C108-C109 \\sim C110-C109 \\sim C111-C112
\\sim C107-C112
 with sigma of 0.02
 O24-C119 \\sim O1A_$1-C120_$1 \\sim C121_$1-O27_$1
 with sigma of 0.02
 C117-C109 \\sim C113-C109 \\sim C117-C116 \\sim C114-C113 \\sim C115-C116
\\sim C115-C114
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
: with sigma of 0.1 and sigma for terminal atoms of 0.2
: with sigma of 0.1 and sigma for terminal atoms of 0.2
4. Rigid body (RIGU) restrains
 O22, C99, O21, C100, C105, C104, C103, C102, C101
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Fixed Sof: C101(0.5) H101(0.5) O136(0.5) H136(0.5) C99(0.5) C102(0.5)
 H102(0.5) C95(0.5) H95(0.5) C100(0.5) C104(0.5) H104(0.5) C103(0.5) H103(0.5)
 C105(0.5) H105(0.5) O21(0.5) C94(0.5) H94(0.5) O18(0.5) C92(0.5) C96(0.5)
 H96(0.5) C93(0.5) C97(0.5) H97(0.5) O22(0.5) O17(0.5) C98(0.5) H98(0.5)
 C109(0.8) H109(0.5) H10A(0.3) C106(0.5) C107(0.5) O26(0.5) C108(0.5) H108(0.5)
 C110(0.5) H110(0.5) C112(0.5) H112(0.5) O25(0.5) C111(0.5) H111(0.5) O1A(0.5)
 H1A(0.5) C120(0.5) H12C(0.5) H12D(0.5) H12E(0.5) O24(0.3) C119(0.3) O27(0.4)
 H27A(0.4) C121(0.4) H12F(0.4) H12G(0.4) H12H(0.4) C117(0.3) H117(0.3)
 C116(0.3) C115(0.3) H115(0.3) C114(0.3) H114(0.3) C113(0.3) H113(0.3) O23(0.3)
6.a Riding coordinates:
 C28(H28A,H28B,H28C), O136(H136), O27(H27A), C121(H12F,H12G,H12H)
6.b Ternary CH refined with riding coordinates:
 C42(H42), C80(H80), C58(H58), C41(H41), C79(H79), C64(H64), C59(H59),
 C63(H63), C11(H11), C10(H10), C27(H27), C26(H26)
6.c Secondary CH2 refined with riding coordinates:
 C46(H46A,H46B), C67(H67A,H67B), C43(H43A,H43B), C81(H81A,H81B), C44(H44A,
 H44B), C68(H68A,H68B), C57(H57A,H57B), C62(H62A,H62B), C84(H84A,H84B),
 C83(H83A,H83B), C65(H65A,H65B), C45(H45A,H45B), C66(H66A,H66B), C82(H82A,H82B),
  C60(H60A,H60B), C12(H12A,H12B), C61(H61A,H61B), C15(H15A,H15B), C30(H30A,
 H30B), C13(H13A,H13B), C0AA(H0AA,H0AB), C31(H31A,H31B), C29(H29A,H29B),
 C14(H14A,H14B)
6.d Aromatic/amide H refined with riding coordinates:
 C36(H36), C3(H3), C5(H5), C49(H49), C53(H53), C7(H7), C9(H9), C1(H1), C8(H8),
 C37(H37), C34(H34), C73(H73), C39(H39), C32(H32), C78(H78), C40(H40), C20(H20),
  C25(H25), C131(H131), C135(H135), C132(H132), C134(H134), C133(H133),
 C124(H124), C125(H125), C101(H101), C89(H89), C87(H87), C126(H126), C128(H128),
  C91(H91), C102(H102), C95(H95), C104(H104), C103(H103), C90(H90), C105(H105),
 C127(H127), C94(H94), C88(H88), C96(H96), C97(H97), C98(H98), C109(H109),
 C109(H10A), C108(H108), C110(H110), C112(H112), C111(H111), C117(H117),
 C115(H115), C114(H114), C113(H113)
6.e Idealised Me refined as rotating group:
 C120(H12C,H12D,H12E)
6.f Idealised tetrahedral OH refined as rotating group:
 O1A(H1A)
;
_shelx_res_checksum              16091
_shelx_hkl_checksum              98261
_olex2_date_sample_data_collection 2019-08-16
_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_PlcyCage138RR_130K
_olex2_submission_special_instructions 'No special instructions were received'