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_7134052
_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         '2(C78 H58 N8 O2 Pt2), 2(C H Cl3), C6 H14'
_chemical_formula_sum            'C164 H132 Cl6 N16 O4 Pt4'
_chemical_formula_weight         3383.91
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-12-06
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-12-06 deposited with the CCDC.	2024-12-10 downloaded from the CCDC.
;
_cell_angle_alpha                94.9910(10)
_cell_angle_beta                 93.2430(10)
_cell_angle_gamma                90.9970(10)
_cell_formula_units_Z            1
_cell_length_a                   11.3270(2)
_cell_length_b                   16.6957(2)
_cell_length_c                   17.5885(3)
_cell_measurement_reflns_used    25378
_cell_measurement_temperature    293(2)
_cell_measurement_theta_max      75.3140
_cell_measurement_theta_min      3.4430
_cell_volume                     3307.45(9)
_computing_cell_refinement       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.72a (Rigaku OD, 2022)'
_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      293(2)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.957
_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    -75.00 -50.00   0.50    0.54    --  -46.17 122.00-155.00   50
  2  \w   -117.00 -83.00   0.50    0.54    --  -46.17-150.00 -38.00   68
  3  \w     15.00  90.00   0.50    0.54    --   46.17-122.00 122.00  150
  4  \w     56.00 104.00   0.50    0.54    --   46.17 150.00   5.00   96
  5  \w     67.00 110.00   0.50    0.54    --   46.17-150.00 -38.00   86
  6  \w   -138.00 -96.00   0.50    2.14    -- -105.02-122.00 122.00   84
  7  \w   -110.00 -78.00   0.50    2.14    -- -105.02 122.00-155.00   64
  8  \w   -128.00 -33.00   0.50    2.14    -- -105.02 150.00   5.00  190
  9  \w    -75.00 -37.00   0.50    2.14    -- -105.02 122.00-155.00   76
 10  \w   -117.00 -92.00   0.50    2.14    -- -105.02-150.00 -38.00   50
 11  \w     89.00 129.00   0.50    2.14    --  105.02 122.00-155.00   80
 12  \w     86.00 111.00   0.50    2.14    --  105.02 150.00   5.00   50
 13  \w     56.00  82.00   0.50    2.14    --  105.02-122.00 122.00   52
 14  \w     32.00 129.00   0.50    2.14    --  105.02-150.00 -38.00  194
 15  \w    -12.00  28.00   0.50    0.54    --  -46.17  19.00-180.00   80
 16  \w   -108.00 -72.00   0.50    0.54    --  -46.17 -57.00-150.00   72
 17  \w    -69.00 -44.00   0.50    0.54    --  -46.17 -57.00-150.00   50
 18  \w    -92.00 -67.00   0.50    0.54    --  -46.17 150.00   5.00   50
 19  \w     24.00 117.00   0.50    0.54    --   46.17  77.00-180.00  186
 20  \w    -18.00  20.00   0.50    0.54    --   46.17 -19.00-120.00   76
 21  \w    -28.00  17.00   0.50    0.54    --   46.17 -19.00-150.00   90
 22  \w    -29.00   9.00   0.50    0.54    --   46.17 -19.00 -30.00   76
 23  \w    -29.00  -3.00   0.50    0.54    --   46.17 -19.00 -60.00   52
 24  \w   -112.00 -55.00   0.50    2.14    -- -105.02 125.00 -60.00  114
 25  \w    -60.00 -35.00   0.50    2.14    -- -105.02  61.00 -60.00   50
 26  \w    -68.00 -39.00   0.50    2.14    -- -105.02  61.00  30.00   58
 27  \w    -73.00 -32.00   0.50    2.14    -- -105.02  61.00 -30.00   82
 28  \w    -73.00 -32.00   0.50    2.14    -- -105.02   0.00 -60.00   82
 29  \w    -76.00 -36.00   0.50    2.14    -- -105.02 125.00 -90.00   80
 30  \w    -72.00 -44.00   0.50    2.14    -- -105.02   0.00-120.00   56
 31  \w   -112.00 -87.00   0.50    2.14    -- -105.02 125.00 -90.00   50
 32  \w    -73.00 -46.00   0.50    2.14    -- -105.02   0.00-180.00   54
 33  \w    -72.00 -36.00   0.50    2.14    -- -105.02  61.00-150.00   72
 34  \w    -75.00 -41.00   0.50    2.14    -- -105.02   0.00  90.00   68
 35  \w    -72.00 -32.00   0.50    2.14    -- -105.02  61.00-120.00   80
 36  \w    -67.00 -42.00   0.50    2.14    -- -105.02   0.00 -90.00   50
 37  \w    -73.00 -32.00   0.50    2.14    -- -105.02  61.00-180.00   82
 38  \w   -111.00 -57.00   0.50    2.14    -- -105.02 125.00  90.00  108
 39  \w    -69.00 -36.00   0.50    2.14    -- -105.02   0.00 120.00   66
 40  \w    -73.00 -33.00   0.50    2.14    -- -105.02   0.00   0.00   80
 41  \w     43.00  69.00   0.50    2.14    --  105.02 -61.00-180.00   52
 42  \w     66.00 102.00   0.50    2.14    --  105.02 -94.00 -30.00   72
 43  \w     33.00  73.00   0.50    2.14    --  105.02 -61.00  30.00   80
 44  \w     85.00 110.00   0.50    2.14    --  105.02-125.00-150.00   50
 45  \w     87.00 153.00   0.50    2.14    --  105.02  77.00  90.00  132
 46  \w     32.00  73.00   0.50    2.14    --  105.02 -61.00 -30.00   82
 47  \w     90.00 169.00   0.50    2.14    --  105.02  61.00 120.00  158
 48  \w     37.00  73.00   0.50    2.14    --  105.02 -61.00   0.00   72
 49  \w     79.00 104.00   0.50    2.14    --  105.02 -94.00   0.00   50
 50  \w     74.00  99.00   0.50    2.14    --  105.02 -94.00 120.00   50
 51  \w     46.00  71.00   0.50    2.14    --  105.02 -94.00 120.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type
'XtaLAB Synergy, Single source at home/near, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0200136000
_diffrn_orient_matrix_UB_12      0.0190727000
_diffrn_orient_matrix_UB_13      -0.0838335000
_diffrn_orient_matrix_UB_21      0.0127315000
_diffrn_orient_matrix_UB_22      0.0905901000
_diffrn_orient_matrix_UB_23      0.0251993000
_diffrn_orient_matrix_UB_31      0.1341794000
_diffrn_orient_matrix_UB_32      -0.0036395000
_diffrn_orient_matrix_UB_33      -0.0096803000
_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  0.0541
_diffrn_reflns_av_unetI/netI     0.0505
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.957
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       21
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            46056
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.957
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.398
_diffrn_reflns_theta_min         2.526
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    9.368
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.46732
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.72a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear dark red'
_exptl_crystal_density_diffrn    1.699
_exptl_crystal_description       plate
_exptl_crystal_F_000             1674
_exptl_crystal_size_max          0.05
_exptl_crystal_size_mid          0.02
_exptl_crystal_size_min          0.02
_refine_diff_density_max         6.250
_refine_diff_density_min         -2.036
_refine_diff_density_rms         0.222
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.098
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     914
_refine_ls_number_reflns         13284
_refine_ls_number_restraints     891
_refine_ls_restrained_S_all      1.063
_refine_ls_R_factor_all          0.0712
_refine_ls_R_factor_gt           0.0627
_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^)+(0.0688P)^2^+55.8941P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1733
_refine_ls_wR_factor_ref         0.1788
_reflns_Friedel_coverage         0.000
_reflns_number_gt                11389
_reflns_number_total             13284
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4cc05684a2.cif
_cod_data_source_block           exp_799_auto
_cod_depositor_comments
'Adding full bibliography for 7134050--7134053.cif.'
_cod_database_code               7134052
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         C85H65N8O2Pt2Cl3
_chemical_oxdiff_usercomment     '150 K'
_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
 Cl-C02P \\sim ClA-C02Q
 with sigma of 0.02
 Cl1-C02P \\sim Cl1A-C02Q
 with sigma of 0.02
 Cl2-C02P \\sim Cl2A-C02Q
 with sigma of 0.02
 Cl-Cl1 \\sim ClA-Cl1A
 with sigma of 0.04
 Cl-Cl2 \\sim ClA-Cl2A
 with sigma of 0.04
 Cl1-Cl2 \\sim Cl1A-Cl2A
 with sigma of 0.04
3. Uiso/Uaniso restraints and constraints
Uanis(C02Q) = Uanis(C02P)
4. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(ClA)=Sof(Cl1A)=Sof(Cl2A)=Sof(C02Q)=Sof(H3)=1-FVAR(1)
 Sof(Cl)=Sof(Cl1)=Sof(Cl2)=Sof(C02P)=Sof(H2)=FVAR(1)
6.a Ternary CH refined with riding coordinates:
 C02P(H2), C02Q(H3)
6.b Secondary CH2 refined with riding coordinates:
 C01G(H01A,H01C), C026(H02,H)
6.c Aromatic/amide H refined with riding coordinates:
 C00J(H00J), C00K(H00K), C00L(H00L), C00O(H00O), C00R(H00R), C00S(H00S),
 C00T(H00T), C00V(H00V), C00W(H00W), C00X(H00X), C00Y(H00Y), C011(H011),
 C017(H017), C019(H019), C01B(H01B), C01E(H01E), C01F(H01F), C01I(H01I),
 C01J(H01J), C01K(H01K), C01O(H01O), C01Q(H01Q), C01R(H01R), C01S(H01S),
 C01X(H01X), C01Z(H01Z), C023(H023), C027(H027), C02A(H02D), C02E(H02H),
 C02F(H02I), C02G(H02J), C02I(H02N), C02K(H02R)
6.d Idealised Me refined as rotating group:
 C024(H02A,H02B,H02C), C029(H1,HA,HB), C02D(H02E,H02F,H02G), C02H(H02K,H02L,
 H02M), C02J(H02O,H02P,H02Q), C02L(H02S,H02T,H02U), C02M(H02V,H02W,H02X),
 C02N(H02Y,HC,HD), C02O(H02Z,HE,HF)
;
_shelx_res_checksum              33977
_shelx_hkl_checksum              29860
_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 2.028
_oxdiff_exptl_absorpt_empirical_full_min 0.553