Optically active cofacial ABCD-Pt(II)-porphyrin dimer exhibits bright circularly polarized phosphorescence.
Inoue, Ryo; Kobayashi, Mayu; Morisaki, Yasuhiro; Chemical communications (Cambridge, England) 61 (2025) 957–960; doi:10.1039/d4cc05684a

data_7134050
_publ_section_title
;
 Optically active cofacial ABCD-Pt(II)-porphyrin dimer exhibits bright
 circularly polarized phosphorescence.
;
_journal_issue                   5
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              957
_journal_page_last               960
_journal_paper_doi               10.1039/d4cc05684a
_journal_volume                  61
_journal_year                    2025
_chemical_formula_moiety         'C78 H58 N8 O2 Pt2, 4(C H Cl3)'
_chemical_formula_sum            'C82 H62 Cl12 N8 O2 Pt2'
_chemical_formula_weight         2006.97
_space_group_crystal_system      orthorhombic
_space_group_IT_number           18
_space_group_name_Hall           'P 2 2ab'
_space_group_name_H-M_alt        'P 21 21 2'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-12-02
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-12-03 deposited with the CCDC.	2024-12-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   19.3188(3)
_cell_length_b                   19.1158(3)
_cell_length_c                   10.62740(10)
_cell_measurement_reflns_used    31879
_cell_measurement_temperature    150
_cell_measurement_theta_max      29.6590
_cell_measurement_theta_min      2.1890
_cell_volume                     3924.64(9)
_computing_cell_refinement       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.40.53 (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.40.53 (Rigaku OD, 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 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      150
_diffrn_detector                 'CCD plate'
_diffrn_measured_fraction_theta_full 0.994
_diffrn_measured_fraction_theta_max 0.949
_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    -88.00  74.00   0.50    0.50    --  -16.00  45.00 220.00  324
  2  \w    -76.00  74.00   0.50    0.50    --  -16.00  45.00 -20.00  300
  3  \w      8.50  74.00   0.50    0.50    --  -16.00  45.00  60.00  131
  4  \w     24.00  64.00   0.50    0.50    --  -16.00  45.00 140.00   80
;
_diffrn_measurement_device       'abstract diffractometer'
_diffrn_measurement_device_type
'dtrek-CrysAlisPro-abstract goniometer imported rigaku-d*trek images'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0146635000
_diffrn_orient_matrix_UB_12      -0.0306287000
_diffrn_orient_matrix_UB_13      -0.0267287000
_diffrn_orient_matrix_UB_21      0.0232561000
_diffrn_orient_matrix_UB_22      0.0024990000
_diffrn_orient_matrix_UB_23      -0.0513810000
_diffrn_orient_matrix_UB_31      0.0243522000
_diffrn_orient_matrix_UB_32      -0.0208422000
_diffrn_orient_matrix_UB_33      0.0330295000
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Mo K\a'
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0359
_diffrn_reflns_av_unetI/netI     0.0292
_diffrn_reflns_Laue_measured_fraction_full 0.994
_diffrn_reflns_Laue_measured_fraction_max 0.949
_diffrn_reflns_limit_h_max       20
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       14
_diffrn_reflns_limit_l_min       -14
_diffrn_reflns_number            38932
_diffrn_reflns_point_group_measured_fraction_full 0.996
_diffrn_reflns_point_group_measured_fraction_max 0.921
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.567
_diffrn_reflns_theta_min         2.362
_diffrn_source                   'fine-focus sealed X-ray tube'
_diffrn_source_type              'Enhance (Mo) X-ray Source'
_exptl_absorpt_coefficient_mu    4.023
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.44040
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.40.53 (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark orange'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.698
_exptl_crystal_description       plate
_exptl_crystal_F_000             1972
_exptl_crystal_preparation       CHCl3/hexane
_exptl_crystal_recrystallization_method CHCl3/hexane
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.3
_exptl_crystal_size_min          0.2
_refine_diff_density_max         0.980
_refine_diff_density_min         -1.067
_refine_diff_density_rms         0.106
_refine_ls_abs_structure_details
;
 Flack x determined using 4047 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   -0.025(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.030
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     526
_refine_ls_number_reflns         10138
_refine_ls_number_restraints     180
_refine_ls_restrained_S_all      1.052
_refine_ls_R_factor_all          0.0328
_refine_ls_R_factor_gt           0.0307
_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^)+(0.0491P)^2^+3.7772P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0772
_refine_ls_wR_factor_ref         0.0784
_reflns_Friedel_coverage         0.757
_reflns_Friedel_fraction_full    0.997
_reflns_Friedel_fraction_max     0.886
_reflns_number_gt                9703
_reflns_number_total             10138
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc05684a2.cif
_cod_data_source_block           20230203-pordimer-anti--chcl3-hex
_cod_depositor_comments
'Adding full bibliography for 7134050--7134053.cif.'
_cod_database_code               7134050
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C82H62Cl12N8O2Pt2
_shelx_estimated_absorpt_t_max   0.500
_shelx_estimated_absorpt_t_min   0.238
_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
 Cl3-C8 \\sim Cl3A-C8A
 with sigma of 0.02
 Cl4-C8 \\sim Cl4A-C8A
 with sigma of 0.02
 Cl5-C8 \\sim Cl5A-C8A
 with sigma of 0.02
 Cl3-Cl4 \\sim Cl3A-Cl4A
 with sigma of 0.04
 Cl3-Cl5 \\sim Cl3A-Cl5A
 with sigma of 0.04
 Cl4-Cl5 \\sim Cl4A-Cl5A
 with sigma of 0.04
 Cl4-C8 \\sim Cl4A-C8A \\sim Cl3A-C8A \\sim Cl3-C8 \\sim Cl5A-C8A \\sim Cl5-C8
 with sigma of 0.01
 Cl2-C10 \\sim Cl2A-C10A
 with sigma of 0.02
 Cl-C10 \\sim ClA-C10A
 with sigma of 0.02
 Cl1-C10 \\sim Cl1A-C10A
 with sigma of 0.02
 Cl2-Cl \\sim Cl2A-ClA
 with sigma of 0.04
 Cl2-Cl1 \\sim Cl2A-Cl1A
 with sigma of 0.04
 Cl-Cl1 \\sim ClA-Cl1A
 with sigma of 0.04
 Cl2A-C10A \\sim Cl2-C10 \\sim Cl-C10 \\sim ClA-C10A \\sim Cl1A-C10A \\sim
Cl1-C10
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Cl3 \\sim Cl4 \\sim Cl5 \\sim C8 \\sim C8A \\sim Cl5A \\sim Cl4A \\sim Cl3A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(Cl2) \\sim Ueq, Uanis(Cl) \\sim Ueq, Uanis(Cl1) \\sim Ueq, Uanis(C10)
\\sim Ueq, Uanis(ClA) \\sim Ueq, Uanis(C10A) \\sim Ueq, Uanis(Cl1A) \\sim Ueq,
Uanis(Cl2A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(Cl3) = Uanis(Cl3A)
Uanis(C10A) = Uanis(C10)
Uanis(Cl1) = Uanis(Cl1A)
Uanis(Cl2) = Uanis(Cl2A)
Uanis(Cl) = Uanis(ClA)
4. Others
 Sof(C8A)=Sof(H8A)=Sof(Cl5A)=Sof(Cl4A)=Sof(Cl3A)=1-FVAR(1)
 Sof(Cl3)=Sof(Cl4)=Sof(Cl5)=Sof(C8)=Sof(H8)=FVAR(1)
 Sof(ClA)=Sof(C10A)=Sof(H10A)=Sof(Cl1A)=Sof(Cl2A)=1-FVAR(2)
 Sof(Cl2)=Sof(Cl)=Sof(Cl1)=Sof(C10)=Sof(H10)=FVAR(2)
5.a Ternary CH refined with riding coordinates:
 C8(H8), C10(H10), C8A(H8A), C10A(H10A)
5.b Aromatic/amide H refined with riding coordinates:
 C008(H008), C00A(H00A), C00E(H00E), C00I(H00I), C00L(H00L), C00P(H00P),
 C00R(H00R), C00S(H00S), C00T(H00T), C00W(H00W), C011(H011), C014(H014),
 C016(H016), C017(H017), C018(H018), C01B(H01G), C01E(H01K)
5.c Idealised Me refined as rotating group:
 C010(H01A,H01B,H01C), C01A(H01D,H01E,H01F), C01C(H01H,H01I,H01J), C01G(H01L,
 H01M,H01N)
;
_shelx_res_checksum              93718
_shelx_hkl_checksum              88889
_olex2_exptl_crystal_mounting_method fiber
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.857
_oxdiff_exptl_absorpt_empirical_full_min 0.593