Synergistic <i>meso</i>-β regulation of porphyrins: squeezing the band gap into the near-infrared I/II region.
Qu, Chulin; Gong, Xinxin; Sun, Yufen; Gao, Hu; Cai, Fangjian; Zhao, Yue; Wu, Fan; Shen, Zhen; Chemical science 15 (2024) 10491–10498; doi:10.1039/d4sc01806k

data_1571784
_publ_section_title
;
 Synergistic <i>meso</i>-&#x3b2; regulation of porphyrins: squeezing the
 band gap into the near-infrared I/II region.
;
_journal_issue                   27
_journal_name_full               'Chemical science'
_journal_page_first              10491
_journal_page_last               10498
_journal_paper_doi               10.1039/d4sc01806k
_journal_volume                  15
_journal_year                    2024
_chemical_formula_moiety         'C96 H108 Cl N4 Si4 Zn, C8 H20 N'
_chemical_formula_sum            'C104 H128 Cl N5 Si4 Zn'
_chemical_formula_weight         1661.29
_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
_atom_sites_solution_primary     dual
_audit_creation_date             2022-08-29
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2024-01-13 deposited with the CCDC.	2024-06-03 downloaded from the CCDC.
;
_cell_angle_alpha                107.001(3)
_cell_angle_beta                 106.988(3)
_cell_angle_gamma                94.445(3)
_cell_formula_units_Z            2
_cell_length_a                   16.0410(10)
_cell_length_b                   17.7484(11)
_cell_length_c                   19.0998(12)
_cell_measurement_reflns_used    9869
_cell_measurement_temperature    193.00
_cell_measurement_theta_max      54.55
_cell_measurement_theta_min      2.30
_cell_volume                     4893.7(5)
_computing_cell_refinement       'SAINT V8.40B (Bruker, 2019)'
_computing_data_collection       'APEX4 V2021.10-0 (Bruker, 2021)'
_computing_data_reduction        'SAINT V8.40B (Bruker, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/2 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      193.00
_diffrn_detector                 CPAD
_diffrn_detector_area_resol_mean 7.41
_diffrn_detector_type            'Bruker PHOTON II'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.994
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Bruker D8 VENTURE Metaljet PHOTON II'
_diffrn_measurement_method       '\w and \f shutterless scans'
_diffrn_measurement_specimen_support 'nylon loop'
_diffrn_radiation_monochromator  'Helios Multi-layer Optic'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           GaK\a
_diffrn_radiation_wavelength     1.34139
_diffrn_reflns_av_R_equivalents  0.0820
_diffrn_reflns_av_unetI/netI     0.0875
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.994
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -23
_diffrn_reflns_number            53920
_diffrn_reflns_point_group_measured_fraction_full 0.994
_diffrn_reflns_point_group_measured_fraction_max 0.994
_diffrn_reflns_theta_full        53.594
_diffrn_reflns_theta_max         53.906
_diffrn_reflns_theta_min         2.229
_diffrn_source                   MetalJet
_diffrn_source_current           2.86
_diffrn_source_power             0.19937059999999998
_diffrn_source_type              'Liquid Metal source'
_diffrn_source_voltage           69.71
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.928
_exptl_absorpt_correction_T_max  0.7512
_exptl_absorpt_correction_T_min  0.5411
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1412 before and 0.0826 after correction.
The Ratio of minimum to maximum transmission is 0.7203.
The \l/2 correction factor is Not present.
;
_exptl_crystal_density_diffrn    1.127
_exptl_crystal_description       block
_exptl_crystal_F_000             1780
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.822
_refine_diff_density_min         -1.332
_refine_diff_density_rms         0.096
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.051
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1230
_refine_ls_number_reflns         17849
_refine_ls_number_restraints     700
_refine_ls_restrained_S_all      1.118
_refine_ls_R_factor_all          0.1918
_refine_ls_R_factor_gt           0.1177
_refine_ls_shift/su_max          0.043
_refine_ls_shift/su_mean         0.003
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1200P)^2^+16.0000P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2874
_refine_ls_wR_factor_ref         0.3321
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8933
_reflns_number_total             17849
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4sc01806k2.cif
_cod_data_source_block           20220716syf2_0m
_cod_depositor_comments
;
The following automatic conversions were performed:

data item '_diffrn_radiation_probe' value 'X-ray' was changed to
'x-ray' in accordance with the
/home/data/users/saulius/crontab/automatic-downloads/rss-feeds/RSC/lib/dictionaries/cif_core.dic
dictionary named 'cif_core.dic' version 2.4.2 last updated on
2011-04-26.

Automatic conversion script
Id: cif_fix_values 8170 2020-07-09 18:12:32Z antanas 

 Adding full bibliography for 1571783--1571784.cif.
;
_cod_database_code               1571784
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.913
_shelx_estimated_absorpt_t_min   0.889
_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
 C105-C111 = C108-C111 = C113-C107 = C113-C112 = C106-C110 = C106-C109
 1.53 with sigma of 0.005
 C117-C121 = C115-C93 = C116-C114 = C119-C118
 1.5 with sigma of 0.005
 C92-C53 = C93-C89 = C81-C1 = C91-C85
 1.5 with sigma of 0.005
 N5-C89 = N5-C85 = N5-C81 = N5-C92
 1.5 with sigma of 0.005
 C94-C82 = C87-C82
 1.53 with sigma of 0.005
 N5-C115 = N5-C114 = N5-C119 = N5-C117
 1.5 with sigma of 0.005
 C103-C102 = C103-C97 = C98-C101 = C101-C95 = C96-C99 = C96-C100
 1.53 with sigma of 0.005
 C121-C117
 1.53 with sigma of 0.005
 C116-N5
 2.6 with sigma of 0.005
 N5-C91
 2.6 with sigma of 0.005
 C110-C109
 2.5 with sigma of 0.005
 N5-C118
 2.6 with sigma of 0.005
 C112-C107
 2.5 with sigma of 0.005
 C108-C105
 2.5 with sigma of 0.005
 C102-C97
 2.5 with sigma of 0.005
 C95-C98
 2.5 with sigma of 0.005
 C100-C99
 2.5 with sigma of 0.005
 C1-N5
 2.6 with sigma of 0.005
 C121-N5
 2.6 with sigma of 0.005
 C81-C1 \\sim C117-C121
 with sigma of 0.02
 N5-C91 \\sim N5-C53 \\sim N5-C1 \\sim N5-C93
 with sigma of 0.02
 C92-C53 \\sim C81-C1 \\sim C91-C85
 with sigma of 0.02
 N5-C92 \\sim N5-C81 \\sim N5-C85
 with sigma of 0.02
 C116-C114 \\sim C91-C85
 with sigma of 0.02
 C115-C93 \\sim C120-C89
 with sigma of 0.02
 N5-C92 \\sim N5-C119
 with sigma of 0.02
 N5-C114 \\sim N5-C85
 with sigma of 0.02
 N5-C81 \\sim N5-C117
 with sigma of 0.02
 N5-C115 \\sim N5-C89
 with sigma of 0.02
 Si5-C58 \\sim Si4-C58
 with sigma of 0.02
 Si5-C111 \\sim Si5-C106 \\sim Si5-C113
 with sigma of 0.02
 Si4-C101 \\sim Si4-C103 \\sim Si4-C96
 with sigma of 0.02
 Si4-C97 \\sim Si4-C102
 with sigma of 0.02
 C106-C111 \\sim C113-C111 \\sim C113-C106
 with sigma of 0.02
 C96-C101 \\sim C103-C101 \\sim C103-C96
 with sigma of 0.02
 Si5-C105 \\sim Si5-C108
 with sigma of 0.02
 C89-C81 \\sim C89-C85 \\sim C85-C81 \\sim C92-C89 \\sim C92-C81 \\sim C92-C85
 with sigma of 0.02
 C119-C118 \\sim C92-C53
 with sigma of 0.02
 C115-C117 \\sim C119-C117 \\sim C115-C119 \\sim C115-C114 \\sim C117-C114
\\sim C119-C114
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
N5 \\sim C1 \\sim C81 \\sim C89 \\sim C117 \\sim C114 \\sim C92 \\sim C115
\\sim C119 \\sim C85 \\sim C120 \\sim C121 \\sim C116 \\sim C53 \\sim C93 \\sim
C118 \\sim C91: within 2A with sigma of 0.005 and sigma for terminal atoms of
0.01 within 2A
Si3 \\sim C77 \\sim C82 \\sim C83 \\sim C86 \\sim C87 \\sim C94 \\sim C104
\\sim C78 \\sim C88: within 2A with sigma of 0.01 and sigma for terminal atoms
of 0.02 within 2A
Si4 \\sim C95 \\sim C96 \\sim C98 \\sim C100 \\sim C101 \\sim Si5 \\sim C105
\\sim C106 \\sim C108 \\sim C109 \\sim C110 \\sim C111 \\sim C99 \\sim C97
\\sim C102 \\sim C103 \\sim C107 \\sim C112 \\sim C113: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
Si2 \\sim C68 \\sim C72 \\sim C73 \\sim C75 \\sim C79 \\sim C80 \\sim C84 \\sim
C90 \\sim C76: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
Uanis(C116) \\sim Ueq, Uanis(C91) \\sim Ueq, Uanis(C121) \\sim Ueq, Uanis(C1)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C116) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
4. Others
 Sof(Si4)=Sof(C95)=Sof(H95A)=Sof(H95B)=Sof(H95C)=Sof(C96)=Sof(H96)=Sof(C97)=
 Sof(H97A)=Sof(H97B)=Sof(H97C)=Sof(C98)=Sof(H98A)=Sof(H98B)=Sof(H98C)=Sof(C99)=
 Sof(H99A)=Sof(H99B)=Sof(H99C)=Sof(C100)=Sof(H10A)=Sof(H10B)=Sof(H10C)=
 Sof(C101)=Sof(H101)=Sof(C102)=Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(C103)=
 Sof(H103)=1-FVAR(1)
 Sof(Si5)=Sof(C105)=Sof(H10J)=Sof(H10K)=Sof(H10L)=Sof(C106)=Sof(H106)=
 Sof(C107)=Sof(H10M)=Sof(H10N)=Sof(H10O)=Sof(C108)=Sof(H10P)=Sof(H10Q)=
 Sof(H10R)=Sof(C109)=Sof(H10S)=Sof(H10T)=Sof(H10U)=Sof(C110)=Sof(H11A)=
 Sof(H11B)=Sof(H11C)=Sof(C111)=Sof(H111)=Sof(C112)=Sof(H11D)=Sof(H11E)=
 Sof(H11F)=Sof(C113)=Sof(H113)=FVAR(1)
 Sof(C93)=Sof(H93A)=Sof(H93B)=Sof(H93C)=Sof(C114)=Sof(H11G)=Sof(H11H)=
 Sof(C115)=Sof(H11I)=Sof(H11J)=Sof(C116)=Sof(H11K)=Sof(H11L)=Sof(H11M)=
 Sof(C117)=Sof(H11N)=Sof(H11O)=Sof(C118)=Sof(H11P)=Sof(H11Q)=Sof(H11R)=
 Sof(C119)=Sof(H11S)=Sof(H11T)=Sof(C121)=Sof(H12D)=Sof(H12E)=Sof(H12F)=1-FVAR(2)
 Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C53)=Sof(H53A)=Sof(H53B)=Sof(H53C)=
 Sof(C81)=Sof(H81A)=Sof(H81B)=Sof(C85)=Sof(H85A)=Sof(H85B)=Sof(C89)=Sof(H89A)=
 Sof(H89B)=Sof(C91)=Sof(H91A)=Sof(H91B)=Sof(H91C)=Sof(C92)=Sof(H92A)=Sof(H92B)=
 Sof(C120)=Sof(H12A)=Sof(H12B)=Sof(H12C)=FVAR(2)
5.a Riding coordinates:
 C1(H1A,H1B,H1C), C93(H93A,H93B,H93C), C94(H94A,H94B,H94C), C109(H10S,H10T,
 H10U), C110(H11A,H11B,H11C), C116(H11K,H11L,H11M), C120(H12A,H12B,H12C),
 C121(H12D,H12E,H12F)
5.b Ternary CH refined with riding coordinates:
 C46(H46), C49(H49), C62(H62), C68(H68), C72(H72), C73(H73), C77(H77),
 C82(H82), C83(H83), C96(H96), C101(H101), C103(H103), C106(H106), C111(H111),
 C113(H113)
5.c Secondary CH2 refined with riding coordinates:
 C81(H81A,H81B), C85(H85A,H85B), C89(H89A,H89B), C92(H92A,H92B), C114(H11G,
 H11H), C115(H11I,H11J), C117(H11N,H11O), C119(H11S,H11T)
5.d Aromatic/amide H refined with riding coordinates:
 C12(H12), C21(H21), C27(H27), C28(H28), C33(H33), C34(H34), C35(H35),
 C36(H36), C37(H37), C38(H38), C42(H42), C43(H43), C44(H44), C50(H50), C52(H52),
  C54(H54), C57(H57), C59(H59), C61(H61), C63(H63), C66(H66), C67(H67),
 C70(H70), C74(H74)
5.e Idealised Me refined as rotating group:
 C53(H53A,H53B,H53C), C55(H55A,H55B,H55C), C60(H60A,H60B,H60C), C64(H64A,H64B,
 H64C), C65(H65A,H65B,H65C), C69(H69A,H69B,H69C), C71(H71A,H71B,H71C), C75(H75A,
 H75B,H75C), C76(H76A,H76B,H76C), C78(H78A,H78B,H78C), C79(H79A,H79B,H79C),
 C80(H80A,H80B,H80C), C84(H84A,H84B,H84C), C86(H86A,H86B,H86C), C87(H87A,H87B,
 H87C), C88(H88A,H88B,H88C), C90(H90A,H90B,H90C), C91(H91A,H91B,H91C), C95(H95A,
 H95B,H95C), C97(H97A,H97B,H97C), C98(H98A,H98B,H98C), C99(H99A,H99B,H99C),
 C100(H10A,H10B,H10C), C102(H10D,H10E,H10F), C104(H10G,H10H,H10I), C105(H10J,
 H10K,H10L), C107(H10M,H10N,H10O), C108(H10P,H10Q,H10R), C112(H11D,H11E,H11F),
 C118(H11P,H11Q,H11R)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              83652
_shelx_hkl_checksum              33257
_shelx_fab_checksum              82362
_olex2_submission_special_instructions 'No special instructions were received'
_site                            XU