Reversible transformation of single-crystal two-dimensional polymer framework for photo/thermal reversible photolithography.
Wang, Hui; Sun, Chuanqi; Jia, Xu; Liu, Hui; Li, Cheng; Zhao, Yingjie; Chemical science 16 (2025) 15734–15741; doi:10.1039/d5sc03359d

data_1575236
_publ_section_title
;
 Reversible transformation of single-crystal two-dimensional polymer
 framework for photo/thermal reversible photolithography.
;
_journal_issue                   34
_journal_name_full               'Chemical science'
_journal_page_first              15734
_journal_page_last               15741
_journal_paper_doi               10.1039/d5sc03359d
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety         'C66 H78 N3 O3, 3(B F4)'
_chemical_formula_sum            'C66 H78 B3 F12 N3 O3'
_chemical_formula_weight         1221.74
_chemical_melting_point          100
_chemical_name_common            heat
_chemical_name_systematic        M1'
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-10-16
_audit_creation_method
;
Olex2 1.3
(compiled 2020.11.12 svn.r5f609507 for OlexSys, GUI svn.r6408)
;
_audit_update_record
;
2025-01-07 deposited with the CCDC.	2025-07-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            6
_cell_length_a                   27.228(3)
_cell_length_b                   27.228(3)
_cell_length_c                   15.692(4)
_cell_measurement_reflns_used    1307
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      68.2410
_cell_measurement_theta_min      3.4060
_cell_volume                     10075(3)
_computing_cell_refinement       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_collection       'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_data_reduction        'CrysAlisPro 1.171.42.84a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.984
_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     -8.00  74.00   0.50    2.87    --   54.65  34.00 139.00  164
  2  \w    -65.00 -40.00   0.50    2.87    -- -102.00  58.00 120.00   50
  3  \w    -77.00 -51.00   0.50    2.87    -- -102.00 121.00  82.00   52
  4  \w     32.00  65.00   0.50    2.87    --  109.31 -58.00 -19.00   66
  5  \w     18.00  56.00   0.50    2.87    --  109.31 -89.00 -12.00   76
  6  \w    -87.00 -49.00   0.50    0.72    --    0.00-167.00 120.00   76
  7  \w    -10.00  26.00   0.50    2.87    --  -54.65  19.00-180.00   72
  8  \w     80.00 135.00   0.50    2.87    --   54.65 125.00  60.00  110
  9  \w     88.00 126.00   0.50    2.87    --   54.65 115.00  -4.00   76
 10  \w    -53.00 -23.00   0.50    2.87    -- -102.00  50.00 -60.00   60
 11  \w    -52.00 -26.00   0.50    2.87    -- -102.00  50.00-120.00   52
 12  \w     39.00  75.00   0.50    2.87    --  109.31 -63.00-120.00   72
 13  \w     32.00  63.00   0.50    2.87    --  109.31 -63.00 -30.00   62
 14  \w     27.00  53.00   0.50    2.87    --  109.31 -50.00   0.00   52
 15  \w     49.00  75.00   0.50    2.87    --  109.31 -63.00-180.00   52
 16  \w     33.00  62.00   0.50    2.87    --  109.31 -63.00  60.00   58
 17  \w     72.00 164.00   0.50    2.87    --  109.31  58.00 120.00  184
 18  \w     28.00  55.00   0.50    2.87    --  109.31 -50.00-180.00   54
 19  \w     71.00 105.00   0.50    2.87    --  109.31 -89.00 -12.00   68
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0484845000
_diffrn_orient_matrix_UB_12      0.0138235000
_diffrn_orient_matrix_UB_13      -0.0633381000
_diffrn_orient_matrix_UB_21      0.0431996000
_diffrn_orient_matrix_UB_22      0.0245575000
_diffrn_orient_matrix_UB_23      0.0732695000
_diffrn_orient_matrix_UB_31      -0.0067846000
_diffrn_orient_matrix_UB_32      -0.0590165000
_diffrn_orient_matrix_UB_33      0.0157218000
_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  0.0421
_diffrn_reflns_av_unetI/netI     0.0416
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       32
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       22
_diffrn_reflns_limit_k_min       -31
_diffrn_reflns_limit_l_max       17
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            8834
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        65.084
_diffrn_reflns_theta_max         65.084
_diffrn_reflns_theta_min         3.383
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    0.805
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.30996
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.84a (Rigaku Oxford Diffraction, 2023)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            tan
_exptl_crystal_density_diffrn    1.208
_exptl_crystal_description       prism
_exptl_crystal_F_000             3852
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: acetic acid and formic acid (3:1 by volume)'
_refine_diff_density_max         0.480
_refine_diff_density_min         -0.275
_refine_diff_density_rms         0.073
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.212
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     244
_refine_ls_number_reflns         3763
_refine_ls_number_restraints     85
_refine_ls_restrained_S_all      1.242
_refine_ls_R_factor_all          0.2382
_refine_ls_R_factor_gt           0.1821
_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^)+(0.0500P)^2^+70.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3212
_refine_ls_wR_factor_ref         0.3454
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2091
_reflns_number_total             3763
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc03359d2.cif
_cod_data_source_block           heat1_auto
_cod_depositor_comments          'Adding full bibliography for 1575236.cif.'
_cod_original_sg_symbol_H-M      'R -3'
_cod_database_code               1575236
_shelx_shelxl_version_number     2018/3
_reflns_odcompleteness_completeness 98.25
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     66.97
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C9-C10 \\sim C19-C12 \\sim C22-C19 \\sim C20-C19 \\sim C21-C19 \\sim C15-C13
\\sim C18-C15 \\sim C16-C15
 \\sim C17-C15 \\sim C8-C5 \\sim C2-C1
 with sigma of 0.01
 F1-B1 \\sim F2-B1 \\sim F4-B1 \\sim F3-B1
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
F2 \\sim B1 \\sim F1 \\sim F3 \\sim F4: within -2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within -2A
4.a Aromatic/amide H refined with riding coordinates:
 C11(H11), C14(H14), C7(H7), C6(H6), C4(H4), C3(H3), C9(H9), C8(H8)
4.b Fitted hexagon refined as free rotating group:
 O1(C12,C11,C10,C14,C13), C2(C7,C6,C5,C4,C3)
4.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C16(H16A,H16B,
 H16C), C22(H22A,H22B,H22C), C21(H21A,H21B,H21C)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_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 2.759
_oxdiff_exptl_absorpt_empirical_full_min 0.254