Porphyrin(2.1.2.1) organopalladium complexes as efficient singlet oxygen sensitizers.
Lv, Xiaojuan; Dong, Yuting; Wu, Jinrong; Jiang, Tao; Chen, Feng; Zhang, Tao; Qiu, Fengxian; Xue, Songlin; Dalton transactions (Cambridge, England : 2003) 53 (2024) 5979–5984; doi:10.1039/d4dt00143e

data_7715252
_publ_section_title
;
 Porphyrin(2.1.2.1) organopalladium complexes as efficient singlet oxygen
 sensitizers.
;
_journal_issue                   13
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              5979
_journal_page_last               5984
_journal_paper_doi               10.1039/d4dt00143e
_journal_volume                  53
_journal_year                    2024
_chemical_formula_moiety         'C50 H42 N4 Pd'
_chemical_formula_sum            'C50 H42 N4 Pd'
_chemical_formula_weight         805.27
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_block_doi                 10.5517/ccdc.csd.cc2hpv8b
_audit_creation_date             2023-10-17
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2023-12-17 deposited with the CCDC.	2024-02-27 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.497(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.6620(7)
_cell_length_b                   12.2502(5)
_cell_length_c                   42.765(2)
_cell_measurement_reflns_used    9925
_cell_measurement_temperature    300.00
_cell_measurement_theta_max      62.605
_cell_measurement_theta_min      3.069
_cell_volume                     8189.7(6)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker SMART APEX II diffractometer'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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      300.00
_diffrn_detector                 'CCD area detector'
_diffrn_detector_area_resol_mean 7.9
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.999
_diffrn_measurement_device       'three-circle diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.1974
_diffrn_reflns_av_unetI/netI     0.1044
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.999
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       14
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       49
_diffrn_reflns_limit_l_min       -49
_diffrn_reflns_number            94131
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.999
_diffrn_reflns_theta_full        63.685
_diffrn_reflns_theta_max         63.685
_diffrn_reflns_theta_min         2.950
_diffrn_source                   'sealed X-ray tube'
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_target            Mo
_diffrn_source_type              'Incoatec I\ms'
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.948
_exptl_absorpt_correction_T_max  0.7531
_exptl_absorpt_correction_T_min  0.4990
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1386 before and 0.0931 after correction.
The Ratio of minimum to maximum transmission is 0.6626.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'metallic dark red'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.306
_exptl_crystal_description       block
_exptl_crystal_F_000             3328
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.09
_exptl_crystal_size_min          0.08
_refine_diff_density_max         3.296
_refine_diff_density_min         -1.011
_refine_diff_density_rms         0.247
_refine_ls_extinction_coef       0.0046(4)
_refine_ls_extinction_expression Fc^*^=kFc[1+0.001xFc^2^\l^3^/sin(2\q)]^-1/4^
_refine_ls_extinction_method     'SHELXL-2019/2 (Sheldrick 2019)'
_refine_ls_goodness_of_fit_ref   1.373
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1282
_refine_ls_number_reflns         13456
_refine_ls_number_restraints     1887
_refine_ls_restrained_S_all      1.300
_refine_ls_R_factor_all          0.2393
_refine_ls_R_factor_gt           0.1578
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3885
_refine_ls_wR_factor_ref         0.4709
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5356
_reflns_number_total             13456
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4dt00143e2.cif
_cod_data_source_block           20231017e
_cod_depositor_comments
'Adding full bibliography for 7715252--7715253.cif.'
_cod_database_code               7715252
_shelx_shelxl_version_number     2019/2
_shelx_estimated_absorpt_t_max   0.743
_shelx_estimated_absorpt_t_min   0.694
_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
 C91-C76 = C91A-C76 = C97-C94 = C97A-C94A = C87A-C84A = C87-C84 = C81A-C61 =
 C81-C61 = C41-C26 = C41A-C26 = C31A-C11 = C31-C11 = C37A-C34A = C37-C34 = C47A-
 C44A = C47-C44
 1.5 with sigma of 0.01
 C98A-C97A = C98-C97 = C99A-C97A = C97A-C101 = C97-C100 = C99-C97 = C48-C47 =
 C48A-C47A = C50A-C47A = C50-C47 = C49A-C47A = C49-C47 = C90A-C87A = C90-C87 =
 C89A-C87A = C89-C87 = C88A-C87A = C88-C87 = C39A-C37A = C39-C37 = C40A-C37A =
 C38A-C37A = C38-C37 = C40-C37
 1.54 with sigma of 0.01
 C88-C89 = C88-C90 = C89-C90
 2.515 with sigma of 0.02
 C98-C99 = C98-C100 = C99-C100
 2.515 with sigma of 0.02
 C38A-C39A = C38A-C40A = C39A-C40A
 2.515 with sigma of 0.02
 C38-C39 = C38-C40 = C39-C40
 2.515 with sigma of 0.02
 C88A-C89A = C88A-C90A = C89A-C90A
 2.515 with sigma of 0.02
 C98A-C99A = C98A-C101 = C99A-C101
 2.515 with sigma of 0.02
 C48-C49 = C48-C50 = C49-C50
 2.515 with sigma of 0.02
 C48A-C49A = C48A-C50A = C49A-C50A
 2.515 with sigma of 0.02
3. Restrained planarity
 C85A, C81A, C82A, C84A, C86A, C83A, C87A, C61
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
5. Others
 Sof(C31A)=Sof(C32A)=Sof(H32A)=Sof(C33A)=Sof(H33A)=Sof(C34A)=Sof(C35A)=
 Sof(H35A)=Sof(C36A)=Sof(H36A)=Sof(C37A)=Sof(C40A)=Sof(H40D)=Sof(H40E)=
 Sof(H40F)=Sof(C39A)=Sof(H39D)=Sof(H39E)=Sof(H39F)=Sof(C38A)=Sof(H38D)=
 Sof(H38E)=Sof(H38F)=1-FVAR(1)
 Sof(C31)=Sof(C32)=Sof(H32)=Sof(C33)=Sof(H33)=Sof(C34)=Sof(C35)=Sof(H35)=
 Sof(C36)=Sof(H36)=Sof(C37)=Sof(C38)=Sof(H38A)=Sof(H38B)=Sof(H38C)=Sof(C39)=
 Sof(H39A)=Sof(H39B)=Sof(H39C)=Sof(C40)=Sof(H40A)=Sof(H40B)=Sof(H40C)=FVAR(1)
 Sof(C41A)=Sof(C42A)=Sof(H42A)=Sof(C43A)=Sof(H43A)=Sof(C44A)=Sof(C45A)=
 Sof(H45A)=Sof(C46A)=Sof(H46A)=Sof(C47A)=Sof(C48A)=Sof(H48D)=Sof(H48E)=
 Sof(H48F)=Sof(C49A)=Sof(H49D)=Sof(H49E)=Sof(H49F)=Sof(C50A)=Sof(H50D)=
 Sof(H50E)=Sof(H50F)=1-FVAR(2)
 Sof(C41)=Sof(C42)=Sof(H42)=Sof(C43)=Sof(H43)=Sof(C44)=Sof(C45)=Sof(H45)=
 Sof(C46)=Sof(H46)=Sof(C47)=Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(H48C)=Sof(C49)=
 Sof(H49A)=Sof(H49B)=Sof(H49C)=Sof(C50)=Sof(H50A)=Sof(H50B)=Sof(H50C)=FVAR(2)
 Sof(C87A)=Sof(C88A)=Sof(H88D)=Sof(H88E)=Sof(H88F)=Sof(C89A)=Sof(H89D)=
 Sof(H89E)=Sof(H89F)=Sof(C90A)=Sof(H90D)=Sof(H90E)=Sof(H90F)=Sof(C81A)=
 Sof(C82A)=Sof(H82A)=Sof(C83A)=Sof(H83A)=Sof(C84A)=Sof(C85A)=Sof(H85A)=
 Sof(C86A)=Sof(H86A)=1-FVAR(3)
 Sof(C81)=Sof(C82)=Sof(H82)=Sof(C83)=Sof(H83)=Sof(C84)=Sof(C85)=Sof(H85)=
 Sof(C86)=Sof(H86)=Sof(C87)=Sof(C88)=Sof(H88A)=Sof(H88B)=Sof(H88C)=Sof(C89)=
 Sof(H89A)=Sof(H89B)=Sof(H89C)=Sof(C90)=Sof(H90A)=Sof(H90B)=Sof(H90C)=FVAR(3)
 Sof(C91A)=Sof(C92A)=Sof(H92A)=Sof(C93A)=Sof(H93A)=Sof(C94A)=Sof(C95A)=
 Sof(H95A)=Sof(C96A)=Sof(H96A)=Sof(C97A)=Sof(C98A)=Sof(H98D)=Sof(H98E)=
 Sof(H98F)=Sof(C99A)=Sof(H99D)=Sof(H99E)=Sof(H99F)=Sof(C101)=Sof(H10D)=
 Sof(H10E)=Sof(H10F)=1-FVAR(4)
 Sof(C91)=Sof(C92)=Sof(H92)=Sof(C93)=Sof(H93)=Sof(C94)=Sof(C95)=Sof(H95)=
 Sof(C96)=Sof(H96)=Sof(C97)=Sof(C98)=Sof(H98A)=Sof(H98B)=Sof(H98C)=Sof(C99)=
 Sof(H99A)=Sof(H99B)=Sof(H99C)=Sof(C100)=Sof(H10A)=Sof(H10B)=Sof(H10C)=FVAR(4)
 Fixed X: C89(0.839469)
6.a Riding coordinates:
 C40A(H40D,H40E,H40F)
6.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C13(H13), C14(H14), C17(H17),
 C18(H18), C19(H19), C20(H20), C23(H23), C24(H24), C28(H28), C29(H29), C32(H32),
  C33(H33), C35(H35), C36(H36), C42(H42), C43(H43), C45(H45), C46(H46),
 C53(H53), C54(H54), C55(H55), C56(H56), C58(H58), C59(H59), C63(H63), C64(H64),
  C67(H67), C68(H68), C69(H69), C70(H70), C73(H73), C74(H74), C78(H78),
 C79(H79), C82(H82), C83(H83), C85(H85), C86(H86), C92(H92), C93(H93), C95(H95),
  C96(H96), C32A(H32A), C33A(H33A), C35A(H35A), C36A(H36A), C42A(H42A),
 C43A(H43A), C45A(H45A), C46A(H46A), C82A(H82A), C83A(H83A), C85A(H85A),
 C86A(H86A), C92A(H92A), C93A(H93A), C95A(H95A), C96A(H96A)
6.c Fitted hexagon refined as free rotating group:
 C31(C32,C33,C34,C35,C36), C41(C42,C43,C44,C45,C46), C81(C82,C83,C84,C85,C86),
 C91(C92,C93,C94,C95,C96), C31A(C32A,C33A,C34A,C35A,C36A), C41A(C42A,C43A,C44A,
 C45A,C46A), C81A(C82A,C83A,C84A,C85A,C86A), C91A(C92A,C93A,C94A,C95A,C96A)
6.d Idealised Me refined as rotating group:
 C38(H38A,H38B,H38C), C39(H39A,H39B,H39C), C40(H40A,H40B,H40C), C48(H48A,H48B,
 H48C), C49(H49A,H49B,H49C), C50(H50A,H50B,H50C), C88(H88A,H88B,H88C), C89(H89A,
 H89B,H89C), C90(H90A,H90B,H90C), C98(H98A,H98B,H98C), C99(H99A,H99B,H99C),
 C100(H10A,H10B,H10C), C39A(H39D,H39E,H39F), C38A(H38D,H38E,H38F), C48A(H48D,
 H48E,H48F), C49A(H49D,H49E,H49F), C50A(H50D,H50E,H50F), C88A(H88D,H88E,H88F),
 C89A(H89D,H89E,H89F), C90A(H90D,H90E,H90F), C98A(H98D,H98E,H98F), C99A(H99D,
 H99E,H99F), C101(H10D,H10E,H10F)
;
_shelx_res_checksum              4624
_olex2_submission_special_instructions 'No special instructions were received'