Curved graphene nanoribbons derived from tetrahydropyrene-based polyphenylenes <i>via</i> one-pot K-region oxidation and Scholl cyclization.
Obermann, Sebastian; Zheng, Wenhao; Melidonie, Jason; Böckmann, Steffen; Osella, Silvio; Arisnabarreta, Nicolás; Guerrero-León, L Andrés; Hennersdorf, Felix; Beljonne, David; Weigand, Jan J.; Bonn, Mischa; De Feyter, Steven; Hansen, Michael Ryan; Wang, Hai I.; Ma, Ji; Feng, Xinliang; Chemical science 14 (2023) 8607–8614; doi:10.1039/d3sc02824k

data_1569585
_publ_section_title
;
 Curved graphene nanoribbons derived from tetrahydropyrene-based
 polyphenylenes <i>via</i> one-pot K-region oxidation and Scholl
 cyclization.
;
_journal_issue                   32
_journal_name_full               'Chemical science'
_journal_page_first              8607
_journal_page_last               8614
_journal_paper_doi               10.1039/d3sc02824k
_journal_volume                  14
_journal_year                    2023
_chemical_formula_moiety         '2.228(C H2 Cl2), C178 H161.5'
_chemical_formula_sum            'C180.23 H165.95 Cl4.45'
_chemical_formula_weight         2489.58
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2022-07-13
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2022-12-15 deposited with the CCDC.	2023-06-20 downloaded from the CCDC.
;
_cell_angle_alpha                75.8276(8)
_cell_angle_beta                 76.6215(9)
_cell_angle_gamma                89.2410(8)
_cell_formula_units_Z            1
_cell_length_a                   9.72613(10)
_cell_length_b                   19.54803(19)
_cell_length_c                   20.00438(18)
_cell_measurement_reflns_used    19834
_cell_measurement_temperature    100.00(10)
_cell_measurement_theta_max      76.2150
_cell_measurement_theta_min      2.8760
_cell_volume                     3583.73(6)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT  (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.5700
_diffrn_detector_type            AtlasS2
_diffrn_measured_fraction_theta_full 1.000
_diffrn_measured_fraction_theta_max 0.987
_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   -109.00 -16.00   0.50    6.00    --  -38.50 -47.00 -70.00  186
  2  \w    -39.00 -14.00   0.50    6.00    --  -38.50  47.00  77.00   50
  3  \w     19.00  51.00   0.50    6.00    --   42.50 -47.00 -70.00   64
  4  \w     18.00 114.00   0.50    6.00    --   42.50  47.00  77.00  192
  5  \w     43.00 133.00   0.50   24.00    --  111.00 -47.00 -70.00  180
  6  \w    143.00 170.00   0.50   24.00    --  111.00  47.00  77.00   54
  7  \w    -87.00  -8.00   0.50    6.00    --  -38.50 125.00  60.00  158
  8  \w    -86.00 -21.00   0.50    6.00    --  -38.50 125.00-120.00  130
  9  \w     33.00 114.00   0.50    6.00    --   42.50  38.00-150.00  162
 10  \w     36.00  69.00   0.50    6.00    --   42.50 -77.00-180.00   66
 11  \w     97.00 146.00   0.50   24.00    --  111.00 125.00   0.00   98
 12  \w     30.00  61.00   0.50   24.00    --  111.00 -94.00 150.00   62
 13  \w    111.00 149.00   0.50   24.00    --  111.00  77.00   0.00   76
 14  \w    143.00 170.00   0.50   24.00    --  111.00 125.00  30.00   54
 15  \w     31.00  85.00   0.50   24.00    --  111.00 -94.00 -60.00  108
 16  \w     91.00 153.00   0.50   24.00    --  111.00  30.00 120.00  124
 17  \w     31.00  57.00   0.50   24.00    --  111.00 -94.00-150.00   52
 18  \w     80.00 107.00   0.50   24.00    --  111.00 -94.00-150.00   54
 19  \w     37.00  81.00   0.50   24.00    --  111.00 -15.00  90.00   88
 20  \w     75.00 111.00   0.50   24.00    --  111.00-125.00-180.00   72
 21  \w     40.00 112.00   0.50   24.00    --  111.00-125.00-150.00  144
 22  \w     70.00 108.00   0.50   24.00    --  111.00-108.00  36.37   76
 23  \w     32.00 107.00   0.50   24.00    --  111.00 -94.00-120.00  150
 24  \w     98.00 137.00   0.50   24.00    --  111.00 125.00  30.00   78
 25  \w     39.00 101.00   0.50   24.00    --  111.00 -94.00  60.00  124
 26  \w     35.00  61.00   0.50   24.00    --  111.00-108.00  36.37   52
 27  \w     82.00 173.00   0.50   24.00    --  111.00  15.00   0.00  182
 28  \w     40.00  65.00   0.50   24.00    --  111.00-125.00  90.00   50
 29  \w     84.00 111.00   0.50   24.00    --  111.00-125.00  90.00   54
 30  \w     40.00  66.00   0.50   24.00    --  111.00 -45.00  30.00   52
 31  \w     70.00  99.00   0.50   24.00    --  111.00 -45.00  30.00   58
 32  \w    103.00 130.00   0.50   24.00    --  111.00 -45.00  30.00   54
 33  \w    100.00 125.00   0.50   24.00    --  111.00  61.00 -60.00   50
 34  \w     94.00 155.00   0.50   24.00    --  111.00 -15.00  90.00  122
 35  \w     79.00 106.00   0.50   24.00    --  111.00-125.00 150.00   54
 36  \w     62.00 108.00   0.50   24.00    --  111.00-125.00-120.00   92
 37  \w     47.00 112.00   0.50   24.00    --  111.00-125.00   0.00  130
 38  \w     75.00 110.00   0.50   24.00    --  111.00-125.00  30.00   70
 39  \w     30.00 107.00   0.50   24.00    --  111.00 -94.00  90.00  154
 40  \w     49.00  76.00   0.50   24.00    --  111.00-125.00 -60.00   54
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, AtlasS2'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.1145548000
_diffrn_orient_matrix_UB_12      0.0476972000
_diffrn_orient_matrix_UB_13      -0.0254907000
_diffrn_orient_matrix_UB_21      0.0745844000
_diffrn_orient_matrix_UB_22      0.0030719000
_diffrn_orient_matrix_UB_23      -0.0775880000
_diffrn_orient_matrix_UB_31      -0.0887608000
_diffrn_orient_matrix_UB_32      -0.0658521000
_diffrn_orient_matrix_UB_33      0.0030153000
_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  0.0258
_diffrn_reflns_av_unetI/netI     0.0334
_diffrn_reflns_Laue_measured_fraction_full 1.000
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       25
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            43621
_diffrn_reflns_point_group_measured_fraction_full 1.000
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.632
_diffrn_reflns_theta_min         2.334
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    1.230
_exptl_absorpt_correction_T_max  1.000
_exptl_absorpt_correction_T_min  0.703
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.154
_exptl_crystal_description       block
_exptl_crystal_F_000             1323
_exptl_crystal_size_max          0.187
_exptl_crystal_size_mid          0.111
_exptl_crystal_size_min          0.07
_refine_diff_density_max         0.388
_refine_diff_density_min         -0.357
_refine_diff_density_rms         0.042
_refine_ls_abs_structure_details
;
 Refined as a perfect inversion twin.
;
_refine_ls_abs_structure_Flack   0.5
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.034
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1968
_refine_ls_number_reflns         19636
_refine_ls_number_restraints     902
_refine_ls_restrained_S_all      1.034
_refine_ls_R_factor_all          0.0548
_refine_ls_R_factor_gt           0.0459
_refine_ls_shift/su_max          0.010
_refine_ls_shift/su_mean         0.001
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0712P)^2^+1.0083P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1216
_refine_ls_wR_factor_ref         0.1317
_reflns_Friedel_coverage         1.000
_reflns_Friedel_fraction_full    1.000
_reflns_Friedel_fraction_max     0.987
_reflns_number_gt                16714
_reflns_number_total             19636
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3sc02824k2.cif
_cod_data_source_block           10
_cod_depositor_comments
'Adding full bibliography for 1569585--1569586.cif.'
_cod_database_code               1569585
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         C180.2H165Cl4.5
_shelx_estimated_absorpt_t_max   0.919
_shelx_estimated_absorpt_t_min   0.803
_reflns_odcompleteness_completeness 99.73
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     74.33
_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
 Cl7-C182 \\sim Cl9-C183
 with sigma of 0.02
 C182-Cl8 \\sim C183-Cl10
 with sigma of 0.02
 Cl7-Cl8 \\sim Cl9-Cl10
 with sigma of 0.04
 C40-C37A \\sim C40-C37B
 with sigma of 0.04
 C38A-C37A \\sim C38B-C37B
 with sigma of 0.02
 C38A-C39A \\sim C38B-C39B
 with sigma of 0.02
 C37A-C39A \\sim C37B-C39B
 with sigma of 0.04
 C40-C35A \\sim C40-C35B
 with sigma of 0.04
 C37A-C35A \\sim C37B-C35B
 with sigma of 0.04
 C38A-C32 \\sim C38B-C32
 with sigma of 0.04
 C35A-C41A \\sim C35B-C41B
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
C170 \\sim C173 \\sim C171 \\sim C172 \\sim C174 \\sim C175 \\sim C176 \\sim
C178 \\sim C186 \\sim C187 \\sim C188 \\sim C189 \\sim C190 \\sim C191: within
2A with sigma of 0.005 and sigma for terminal atoms of 0.01 within 2A
C1B \\sim C6B \\sim C5B \\sim C4B \\sim C93B \\sim C3B \\sim C94B \\sim C2B
\\sim C92B \\sim C91B \\sim C6A \\sim C1A \\sim C2A \\sim C3A \\sim C92A \\sim
C4A \\sim C91A \\sim C5A \\sim C93A \\sim C94A \\sim C7 \\sim C97 \\sim C96
\\sim C95: within 2A with sigma of 0.005 and sigma for terminal atoms of 0.01
within 2A
C29 \\sim C32 \\sim C42A \\sim C43A \\sim C42B \\sim C43B: within 2A with sigma
of 0.005 and sigma for terminal atoms of 0.01 within 2A
Cl7 \\sim Cl8 \\sim C182 \\sim Cl9 \\sim Cl10 \\sim C183: within 2A with sigma
of 0.01 and sigma for terminal atoms of 0.02 within 2A
C168 \\sim C169 \\sim C184 \\sim C185: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
C33 \\sim C36 \\sim C34A \\sim C35A \\sim C37A \\sim C38A \\sim C39A \\sim C41A
\\sim C34B \\sim C35B \\sim C37B \\sim C38B \\sim C39B \\sim C41B: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
4. Same fragment restrains
{C6B, C5B, C4B, C3B, C2B, C1B, C94B, C93B, C92B, C91B} sigma for 1-2: 0.02,
1-3: 0.02
as in
{C1A, C2A, C3A, C4A, C5A, C6A, C91A, C92A, C93A, C94A}
{C34B, C35B, C37B, C38B, C39B, C41B} sigma for 1-2: 0.02, 1-3: 0.02
as in
{C34A, C35A, C37A, C38A, C39A, C41A}
{C186, C187, C188, C189, C190, C191} sigma for 1-2: 0.02, 1-3: 0.02
as in
{C171, C172, C174, C175, C176, C178}
{Cl3, Cl4, C180} sigma for 1-2: 0.02, 1-3: 0.02
as in
{Cl7, Cl8, C182}
5. Others
 Sof(Cl5)=Sof(Cl6)=Sof(C181)=Sof(H18G)=Sof(H18H)=FVAR(1)
 Sof(Cl3)=Sof(Cl4)=Sof(C180)=Sof(H18A)=Sof(H18B)=FVAR(2)
 Sof(Cl9)=Sof(Cl10)=Sof(C183)=Sof(H18E)=Sof(H18F)=1-FVAR(3)
 Sof(Cl7)=Sof(Cl8)=Sof(C182)=Sof(H18C)=Sof(H18D)=FVAR(3)
 Sof(C42B)=Sof(H42B)=Sof(C43B)=Sof(H43B)=1-FVAR(4)
 Sof(C42A)=Sof(H42A)=Sof(C43A)=Sof(H43A)=FVAR(4)
 Sof(C184)=Sof(H184)=Sof(C185)=Sof(H185)=1-FVAR(5)
 Sof(C168)=Sof(H168)=Sof(C169)=Sof(H169)=FVAR(5)
 Sof(C34B)=Sof(C35B)=Sof(H35B)=Sof(C37B)=Sof(H37B)=Sof(C38B)=Sof(C39B)=
 Sof(H39D)=Sof(H39E)=Sof(H39F)=Sof(C41B)=Sof(H41D)=Sof(H41E)=Sof(H41F)=1-FVAR(6)
 Sof(C34A)=Sof(C35A)=Sof(H35A)=Sof(C37A)=Sof(H37A)=Sof(C38A)=Sof(C39A)=
 Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C41A)=Sof(H41A)=Sof(H41B)=Sof(H41C)=FVAR(6)
 Sof(C186)=Sof(C187)=Sof(H187)=Sof(C188)=Sof(H188)=Sof(C189)=Sof(C190)=
 Sof(H19A)=Sof(H19B)=Sof(H19C)=Sof(C191)=Sof(H19D)=Sof(H19E)=Sof(H19F)=1-FVAR(7)
 Sof(C171)=Sof(C172)=Sof(H172)=Sof(C174)=Sof(H174)=Sof(C175)=Sof(C176)=
 Sof(H17D)=Sof(H17E)=Sof(H17F)=Sof(C178)=Sof(H17G)=Sof(H17H)=Sof(H17I)=FVAR(7)
 Fixed Sof: H89(0.5) C1A(0.5) H1A(0.5) C2A(0.5) C3A(0.5) C4A(0.5) C5A(0.5)
 C6A(0.5) H6A(0.5) C91A(0.5) H91A(0.5) H91B(0.5) C92A(0.5) H92A(0.5) H92B(0.5)
 C93A(0.5) H93A(0.5) H93B(0.5) C94A(0.5) H94A(0.5) H94B(0.5) C6B(0.5) H6B(0.5)
 C5B(0.5) C4B(0.5) C3B(0.5) C2B(0.5) C1B(0.5) H1B(0.5) C94B(0.5) H94C(0.5)
 H94D(0.5) C93B(0.5) H93C(0.5) H93D(0.5) C92B(0.5) H92C(0.5) H92D(0.5)
 C91B(0.5) H91C(0.5) H91D(0.5)
6.a Secondary CH2 refined with riding coordinates:
 C179(H17J,H17K), C180(H18A,H18B), C91A(H91A,H91B), C92A(H92A,H92B), C93A(H93A,
 H93B), C94A(H94A,H94B), C94B(H94C,H94D), C93B(H93C,H93D), C92B(H92C,H92D),
 C91B(H91C,H91D), C182(H18C,H18D), C183(H18E,H18F), C181(H18G,H18H)
6.b Aromatic/amide H refined with riding coordinates:
 C11(H11), C12(H12), C16(H16), C18(H18), C23(H23), C24(H24), C30(H30),
 C31(H31), C45(H45), C46(H46), C50(H50), C52(H52), C57(H57), C58(H58), C60(H60),
  C61(H61), C63(H63), C64(H64), C67(H67), C69(H69), C75(H75), C76(H76),
 C78(H78), C79(H79), C82(H82), C84(H84), C89(H89), C96(H96), C104(H104),
 C105(H105), C107(H107), C108(H108), C111(H111), C113(H113), C120(H120),
 C121(H121), C125(H125), C127(H127), C132(H132), C133(H133), C135(H135),
 C136(H136), C140(H140), C142(H142), C147(H147), C148(H148), C150(H150),
 C151(H151), C153(H153), C154(H154), C157(H157), C159(H159), C165(H165),
 C166(H166), C1A(H1A), C6A(H6A), C35A(H35A), C37A(H37A), C42A(H42A), C43A(H43A),
  C168(H168), C169(H169), C172(H172), C174(H174), C6B(H6B), C1B(H1B),
 C35B(H35B), C37B(H37B), C42B(H42B), C43B(H43B), C184(H184), C185(H185),
 C187(H187), C188(H188)
6.c Idealised Me refined as rotating group:
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C40(H40A,H40B,
 H40C), C54(H54A,H54B,H54C), C55(H55A,H55B,H55C), C56(H56A,H56B,H56C), C71(H71A,
 H71B,H71C), C72(H72A,H72B,H72C), C73(H73A,H73B,H73C), C86(H86A,H86B,H86C),
 C87(H87A,H87B,H87C), C88(H88A,H88B,H88C), C115(H11A,H11B,H11C), C116(H11D,H11E,
 H11F), C117(H11G,H11H,H11I), C129(H12A,H12B,H12C), C130(H13A,H13B,H13C),
 C131(H13D,H13E,H13F), C144(H14A,H14B,H14C), C145(H14D,H14E,H14F), C146(H14G,
 H14H,H14I), C161(H16A,H16B,H16C), C162(H16D,H16E,H16F), C163(H16G,H16H,H16I),
 C177(H17A,H17B,H17C), C39A(H39A,H39B,H39C), C41A(H41A,H41B,H41C), C176(H17D,
 H17E,H17F), C178(H17G,H17H,H17I), C39B(H39D,H39E,H39F), C41B(H41D,H41E,H41F),
 C190(H19A,H19B,H19C), C191(H19D,H19E,H19F)
;
_shelx_res_checksum              38978
_shelx_hkl_checksum              48263
_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 1.494
_oxdiff_exptl_absorpt_empirical_full_min 0.798