Near-infrared (NIR)-responsive activation of Ru-benziphthalocyanine complexes via singlet-triplet transition
Takayama, Orie; Toriumi, Naoyuki; Hanaoka, Kenjiro; Uchiyama, Masanobu; Chemical Science  (2026) –; doi:10.1039/D5SC09646D

data_1576846
_publ_section_title
;
 Near-infrared (NIR)-responsive activation of Ru-benziphthalocyanine
 complexes <i>via</i> singlet-triplet transition.
;
_journal_issue                   19
_journal_name_full               'Chemical science'
_journal_page_first              9600
_journal_page_last               9608
_journal_paper_doi               10.1039/d5sc09646d
_journal_volume                  17
_journal_year                    2026
_chemical_formula_moiety         'C16 H24 N3 Ru, C H6 B11 Br6'
_chemical_formula_sum            'C17 H30 B11 Br6 N3 Ru'
_chemical_formula_weight         975.88
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-10-30
_audit_creation_method
;
Olex2 1.5-ac6-012
(compiled 2023.08.24 svn.re1ec1418 for Rigaku Oxford Diffraction, GUI svn.r6817)
;
_audit_update_record
;
2025-07-12 deposited with the CCDC.	2026-03-10 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   13.6340(7)
_cell_length_b                   17.5899(10)
_cell_length_c                   13.8373(8)
_cell_measurement_reflns_used    3505
_cell_measurement_temperature    123.15
_cell_measurement_theta_max      73.8340
_cell_measurement_theta_min      4.0520
_cell_volume                     3318.5(3)
_computing_cell_refinement       'CrysAlisPro 1.171.43.98a (Rigaku OD, 2023)'
_computing_data_collection
'CrysAlisPro system (CCD 43.98a 64-bit (release 24-11-2023))'
_computing_data_reduction        'CrysAlisPro 1.171.43.98a (Rigaku OD, 2023)'
_computing_molecular_graphics    'Olex2 1.5-ac6-012 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-ac6-012 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/1 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      123.15
_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 0.998
_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    -21.00  25.00   0.50   30.00    --   47.88 -39.00  73.00   92
  2  \w     65.00 120.00   0.50   30.00    --   47.88 140.00  93.00  110
  3  \w    -97.00 -52.00   0.50   50.00    -- -106.00 130.00 -79.00   90
  4  \w    105.00 164.00   0.50   50.00    --  107.43  82.00  36.00  118
  5  \w     42.00 116.00   0.50   50.00    --  107.43-130.00-151.00  148
  6  \w    -14.00  25.00   0.50   30.00    --  -47.88  19.00  30.00   78
  7  \w    -23.00  16.00   0.50   30.00    --   47.88 -19.00-180.00   78
  8  \w    -20.00   8.00   0.50   30.00    --   47.88 -19.00-150.00   56
  9  \w    -63.00 -35.00   0.50   50.00    -- -106.00  57.00  30.00   56
 10  \w    -67.00 -42.00   0.50   50.00    -- -106.00  57.00-120.00   50
 11  \w   -122.00 -57.00   0.50   50.00    -- -106.00  77.00 120.00  130
 12  \w    -65.00 -40.00   0.50   50.00    -- -106.00  57.00 -90.00   50
 13  \w    -65.00 -37.00   0.50   50.00    -- -106.00  57.00 -30.00   56
 14  \w     35.00  60.00   0.50   50.00    --  107.43 -57.00-180.00   50
 15  \w     35.00  67.00   0.50   50.00    --  107.43 -57.00  90.00   64
 16  \w     35.00  60.00   0.50   50.00    --  107.43 -57.00  60.00   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      -0.0489449000
_diffrn_orient_matrix_UB_12      0.0372008000
_diffrn_orient_matrix_UB_13      0.0884328000
_diffrn_orient_matrix_UB_21      0.0276935000
_diffrn_orient_matrix_UB_22      0.0791478000
_diffrn_orient_matrix_UB_23      -0.0391440000
_diffrn_orient_matrix_UB_31      -0.0980778000
_diffrn_orient_matrix_UB_32      0.0036876000
_diffrn_orient_matrix_UB_33      -0.0551523000
_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  0.0583
_diffrn_reflns_av_unetI/netI     0.0548
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -16
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       12
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            11968
_diffrn_reflns_point_group_measured_fraction_full 0.799
_diffrn_reflns_point_group_measured_fraction_max 0.799
_diffrn_reflns_theta_full        67.078
_diffrn_reflns_theta_max         67.078
_diffrn_reflns_theta_min         4.065
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    12.394
_exptl_absorpt_correction_T_max  0.936
_exptl_absorpt_correction_T_min  0.814
_exptl_absorpt_correction_type   gaussian
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.98a (Rigaku Oxford Diffraction, 2023)
Numerical absorption correction based on gaussian integration over
a multifaceted crystal model
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.953
_exptl_crystal_description       block
_exptl_crystal_F_000             1848
_exptl_crystal_size_max          0.08
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.06
_refine_diff_density_max         1.665
_refine_diff_density_min         -1.051
_refine_diff_density_rms         0.161
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.28(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.028
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     327
_refine_ls_number_reflns         4739
_refine_ls_number_restraints     230
_refine_ls_restrained_S_all      1.004
_refine_ls_R_factor_all          0.1035
_refine_ls_R_factor_gt           0.0728
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1502P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1972
_refine_ls_wR_factor_ref         0.2221
_reflns_Friedel_coverage         0.532
_reflns_Friedel_fraction_full    0.581
_reflns_Friedel_fraction_max     0.581
_reflns_number_gt                3203
_reflns_number_total             4739
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc09646d2.cif
_cod_data_source_block           ot237-rucp_auto
_cod_depositor_comments
'Adding full bibliography for 1576846--1576847.cif.'
_cod_database_code               1576846
_shelx_shelxl_version_number     2018/1
_chemical_oxdiff_formula         'C117 H30 B11 N3 Br6 Ru '
_shelx_estimated_absorpt_t_max   0.523
_shelx_estimated_absorpt_t_min   0.437
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All B(H) groups, All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 H00K_$1-H00R
 -2 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
C00A \\sim C00S \\sim N008: within 1.7A with sigma of 0.04 and sigma for
terminal atoms of 0.08 within 1.7A
B00D \\sim B00K \\sim B00L \\sim B00E \\sim B00M \\sim B00T \\sim B00N \\sim
B00F \\sim B00Z \\sim B00Q \\sim B00W: within 1.7A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 1.7A
C00I \\sim B00M \\sim B00E \\sim B00W \\sim B00Q \\sim B00N \\sim B00T \\sim
B00D \\sim B00K \\sim B00L \\sim B00Z \\sim B00F: within 1.7A with sigma of
0.04 and sigma for terminal atoms of 0.08 within 1.7A
4. Rigid body (RIGU) restrains
 B00Q, C00I, B00W, B00E, B00L, B00Z, B00K, B00M, B00D, B00T, B00N, B00F
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5.a :
 C19(C009,C00G,C00H,C00U,C11,C00V,C00R,C17,C00X)
5.b Me refined with riding coordinates:
 C00X(H00P,H00Q,H00R)
5.c Idealised Me refined as rotating group:
 C00C(H00A,H00B,H00C), C00O(H00D,H00E,H00F), C00S(H00G,H00H,H00I), C11(H11A,
 H11B,H11C), C00V(H00J,H00K,H00L), C00R(H00M,H00N,H00O), C17(H17A,H17B,H17C)
5.d Boron cage BH refined with riding coordinates:
 B00E(H00S), C00I(H00T), B00M(H00U), B00N(H00V), B00Q(H00W), B00W(H00X)
;
_shelx_res_checksum              98881
_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 2.030
_oxdiff_exptl_absorpt_empirical_full_min 0.527