Aromatic Heterobicycle-Fused Porphyrins: Impact on Aromaticity and Excited State Electron Transfer Leading to Long-Lived Charge Separation
Moss, Austen; Jang, Youngwoo B.; Arvidson, Jacob; Nesterov, Vladimir; D'Souza, Francis; Wang, Hong; Chemical Science  (2022) –; doi:10.1039/D2SC03238D

data_1567469
_publ_section_title
;
 Aromatic Heterobicycle-Fused Porphyrins: Impact on Aromaticity and
 Excited State Electron Transfer Leading to Long-Lived Charge Separation
;
_journal_name_full               'Chemical Science'
_journal_paper_doi               10.1039/D2SC03238D
_journal_year                    2022
_chemical_formula_moiety
'I, C92 H109 N6 O2 Zn, C6 H14, 2[H2O], 1[C6H14]'
_chemical_formula_sum            'C104 H141 I N6 O4 Zn'
_chemical_formula_weight         1731.52
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2021-09-08
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.03.28 svn.rd84adfe8 for Rigaku Oxford Diffraction, GUI svn.r6032)
;
_audit_update_record
;
2022-05-15 deposited with the CCDC.	2022-08-12 downloaded from the CCDC.
;
_cell_angle_alpha                90.976(3)
_cell_angle_beta                 92.533(3)
_cell_angle_gamma                95.704(3)
_cell_formula_units_Z            2
_cell_length_a                   9.3273(4)
_cell_length_b                   15.4601(6)
_cell_length_c                   34.2082(10)
_cell_measurement_reflns_used    9719
_cell_measurement_temperature    220.0(8)
_cell_measurement_theta_max      74.1920
_cell_measurement_theta_min      3.1480
_cell_volume                     4902.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.41.116a (Rigaku OD, 2021)'
_computing_data_collection       'CrysAlisPro 1.171.41.116a (Rigaku OD, 2021)'
_computing_data_reduction        'CrysAlisPro 1.171.41.116a (Rigaku OD, 2021)'
_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 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      220.0(8)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.987
_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   -108.00 -42.00   0.50   10.00    --  -46.79-175.00 160.00  132
  2  \w   -103.00 -78.00   0.50   10.00    --  -46.79 175.00 167.00   50
  3  \w    -49.00  -4.00   0.50   10.00    --  -46.79 114.00  29.00   90
  4  \w     36.00  86.00   0.50   10.00    --   46.79-114.00 -61.00  100
  5  \w     64.00 119.00   0.50   10.00    --   46.79 175.00 167.00  110
  6  \w   -111.00 -86.00   0.50   45.00    --  -91.75-175.00 160.00   50
  7  \w    -63.00 -37.00   0.50   45.00    --  -91.75 114.00  29.00   52
  8  \w   -126.00 -93.00   0.50   45.00    --  -91.75-114.00 -61.00   66
  9  \w   -114.00 -69.00   0.50   45.00    --  -91.75 175.00 167.00   90
 10  \w     81.00 106.00   0.50   45.00    --  102.69 175.00 167.00   50
 11  \w     96.00 147.00   0.50   45.00    --  102.69-175.00 160.00  102
 12  \w    138.00 163.00   0.50   45.00    --  102.69 114.00  29.00   50
 13  \w     59.00  85.00   0.50   45.00    --  102.69-175.00 160.00   52
 14  \w     32.00 110.00   0.50   45.00    --  102.69-114.00 -61.00  156
 15  \w   -118.00 -85.00   0.50   10.00    --  -46.79 -77.00  30.00   66
 16  \w   -119.00 -86.00   0.50   10.00    --  -46.79 -77.00 120.00   66
 17  \w   -118.00 -90.00   0.50   10.00    --  -46.79 -77.00   0.00   56
 18  \w   -119.00 -87.00   0.50   10.00    --  -46.79 -77.00  60.00   64
 19  \w   -116.00 -87.00   0.50   10.00    --  -46.79 -77.00 -90.00   58
 20  \w   -118.00 -85.00   0.50   10.00    --  -46.79 -77.00 -60.00   66
 21  \w   -119.00 -85.00   0.50   10.00    --  -46.79 -77.00 -30.00   68
 22  \w     65.00  90.00   0.50   10.00    --   46.79-175.00 160.00   50
 23  \w     91.00 116.00   0.50   10.00    --   46.79  77.00-180.00   50
 24  \w    -20.00   7.00   0.50   10.00    --   46.79 -19.00-120.00   54
 25  \w   -160.00-134.00   0.50   45.00    --  -91.75-125.00-150.00   52
 26  \w   -158.00 -81.00   0.50   45.00    --  -91.75-125.00-120.00  154
 27  \w    -64.00 -30.00   0.50   45.00    --  -91.75  77.00-150.00   68
 28  \w    -81.00 -32.00   0.50   45.00    --  -91.75  61.00-180.00   98
 29  \w    -45.00 -18.00   0.50   45.00    --  -91.75  30.00 -30.00   54
 30  \w   -111.00 -86.00   0.50   45.00    --  -91.75-125.00-150.00   50
 31  \w   -114.00 -87.00   0.50   45.00    --  -91.75  77.00-150.00   54
 32  \w    -61.00 -32.00   0.50   45.00    --  -91.75  45.00   0.00   58
 33  \w    -45.00 -17.00   0.50   45.00    --  -91.75  30.00 120.00   56
 34  \w    -44.00 -17.00   0.50   45.00    --  -91.75  30.00  90.00   54
 35  \w    -45.00 -18.00   0.50   45.00    --  -91.75  30.00 -90.00   54
 36  \w   -164.00-120.00   0.50   45.00    --  -91.75 -30.00 -60.00   88
 37  \w    -44.00 -17.00   0.50   45.00    --  -91.75  30.00 -60.00   54
 38  \w    -43.00 -17.00   0.50   45.00    --  -91.75  30.00   0.00   52
 39  \w   -163.00 -78.00   0.50   45.00    --  -91.75 -45.00   0.00  170
 40  \w     90.00 172.00   0.50   45.00    --  102.69  45.00 120.00  164
 41  \w     82.00 112.00   0.50   45.00    --  102.69-125.00  60.00   60
 42  \w     95.00 136.00   0.50   45.00    --  102.69 125.00   0.00   82
 43  \w     30.00  93.00   0.50   45.00    --  102.69 -77.00  60.00  126
 44  \w     69.00 110.00   0.50   45.00    --  102.69-125.00-150.00   82
 45  \w     29.00  54.00   0.50   45.00    --  102.69 -61.00 150.00   50
 46  \w     38.00 105.00   0.50   45.00    --  102.69-125.00 -90.00  134
 47  \w     87.00 112.00   0.50   45.00    --  102.69-125.00-180.00   50
 48  \w     29.00  58.00   0.50   45.00    --  102.69 -61.00-180.00   58
 49  \w     49.00  75.00   0.50   45.00    --  102.69-125.00-180.00   52
 50  \w     83.00 108.00   0.50   45.00    --  102.69-107.00-148.46   50
 51  \w     95.00 171.00   0.50   45.00    --  102.69 125.00 150.00  152
 52  \w     29.00  55.00   0.50   45.00    --  102.69-107.00-148.46   52
 53  \w     81.00 106.00   0.50   45.00    --  102.69-125.00-120.00   50
 54  \w     32.00 105.00   0.50   45.00    --  102.69 -94.00 -60.00  146
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0456747865
_diffrn_orient_matrix_UB_12      -0.0099417537
_diffrn_orient_matrix_UB_13      0.0425514471
_diffrn_orient_matrix_UB_21      -0.1541422583
_diffrn_orient_matrix_UB_22      0.0187980943
_diffrn_orient_matrix_UB_23      -0.0127349472
_diffrn_orient_matrix_UB_31      -0.0420117243
_diffrn_orient_matrix_UB_32      -0.0978834282
_diffrn_orient_matrix_UB_33      -0.0077623256
_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  0.0763
_diffrn_reflns_av_unetI/netI     0.0606
_diffrn_reflns_Laue_measured_fraction_full 0.987
_diffrn_reflns_Laue_measured_fraction_max 0.987
_diffrn_reflns_limit_h_max       11
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       12
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       40
_diffrn_reflns_limit_l_min       -40
_diffrn_reflns_number            59348
_diffrn_reflns_point_group_measured_fraction_full 0.987
_diffrn_reflns_point_group_measured_fraction_max 0.987
_diffrn_reflns_theta_full        66.600
_diffrn_reflns_theta_max         66.600
_diffrn_reflns_theta_min         4.770
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.235
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.88344
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.116a (Rigaku Oxford Diffraction, 2021)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark purple'
_exptl_crystal_density_diffrn    1.197
_exptl_crystal_description       plate
_exptl_crystal_F_000             1884
_exptl_crystal_size_max          0.07
_exptl_crystal_size_mid          0.045
_exptl_crystal_size_min          0.01
_refine_diff_density_max         1.340
_refine_diff_density_min         -1.829
_refine_diff_density_rms         0.101
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     993
_refine_ls_number_reflns         17099
_refine_ls_number_restraints     67
_refine_ls_restrained_S_all      1.045
_refine_ls_R_factor_all          0.1373
_refine_ls_R_factor_gt           0.1157
_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^)+(0.1911P)^2^+11.9857P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3237
_refine_ls_wR_factor_ref         0.3407
_reflns_Friedel_coverage         0.000
_reflns_number_gt                12342
_reflns_number_total             17099
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2sc03238d2.cif
_cod_data_source_block           triclinicmono09072021
_cod_database_code               1567469
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C89 H101 N6 Zn I'
_shelx_estimated_absorpt_t_max   0.968
_shelx_estimated_absorpt_t_min   0.805
_reflns_odcompleteness_completeness 96.87
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     69.95
_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
 C1B-C2B
 1.51 with sigma of 0.01
 O2-C1C
 1.35 with sigma of 0.01
 C1C-C2C
 1.51 with sigma of 0.01
 O2-C1B
 1.35 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Uanis(C44) \\sim Ueq, Uanis(C45) \\sim Ueq, Uanis(C46) \\sim Ueq, Uanis(C47)
\\sim Ueq, Uanis(C48) \\sim Ueq, Uanis(C49) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C1B) = Uanis(C2B) = Uanis(C1C) = Uanis(C2C)
4. Rigid body (RIGU) restrains
 C1A, C2A, C3A, C4A, C5A, C6A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
5. Others
 Sof(C2C)=Sof(H2CA)=Sof(H2CB)=Sof(H2CC)=Sof(C1C)=Sof(H1CA)=Sof(H1CB)=1-FVAR(1)
 Sof(C2B)=Sof(H2BA)=Sof(H2BB)=Sof(H2BC)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=FVAR(1)
6.a Rotating group:
 O2(H2)
6.b Secondary CH2 refined with riding coordinates:
 C2A(H2AA,H2AB), C3A(H3AA,H3AB), C4A(H4AA,H4AB), C5A(H5AA,H5AB), C1B(H1BA,
 H1BB), C1C(H1CA,H1CB)
6.c Aromatic/amide H refined with riding coordinates:
 C2(H2A), C3(H3), C7(H7), C8(H8), C12(H12), C13(H13), C18(H18), C21(H21),
 C26(H26), C28(H28), C30(H30), C32(H32), C34(H34), C36(H36), C38(H38), C40(H40),
  C42(H42), C45(H45), C46(H46), C47(H47), C48(H48), C53(H53), C55(H55),
 C57(H57), C82(H82)
6.d Fitted hexagon refined as free rotating group:
 C44(C45,C46,C47,C48,C49)
6.e Idealised Me refined as rotating group:
 C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C59(H59A,H59B,H59C), C60(H60A,H60B,
 H60C), C61(H61A,H61B,H61C), C63(H63A,H63B,H63C), C64(H64A,H64B,H64C), C65(H65A,
 H65B,H65C), C67(H67A,H67B,H67C), C68(H68A,H68B,H68C), C69(H69A,H69B,H69C),
 C71(H71A,H71B,H71C), C72(H72A,H72B,H72C), C73(H73A,H73B,H73C), C75(H75A,H75B,
 H75C), C76(H76A,H76B,H76C), C77(H77A,H77B,H77C), C79(H79A,H79B,H79C), C80(H80A,
 H80B,H80C), C81(H81A,H81B,H81C), C84(H84A,H84B,H84C), C85(H85A,H85B,H85C),
 C86(H86A,H86B,H86C), C88(H88A,H88B,H88C), C89(H89A,H89B,H89C), C90(H90A,H90B,
 H90C), C1A(H1AA,H1AB,H1AC), C6A(H6AA,H6AB,H6AC), C2B(H2BA,H2BB,H2BC), C2C(H2CA,
 H2CB,H2CC)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 177 electrons were
found in a volume of 727\%A^3 in 2 voids per unit cell.
This is consistent with the presence of 2[H2O], 1[C6H14] 
per Formula Unit which account for 140 electrons 
per unit cell.
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              81257
_shelx_hkl_checksum              36766
_shelx_fab_checksum              53170
_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 1.434
_oxdiff_exptl_absorpt_empirical_full_min 0.472