Observation of Proton Transfer Coupled Spin Transition and Trapping of Photoinduced Metastable Proton Transfer State in an Fe(II) Complex.
Nakanishi, Takumi; Hori, Yuta; Sato, Hiroyasu; Wu, Shu-Qi; Okazawa, Atsushi; Kojima, Norimichi; Yamamoto, Takashi; Einaga, Yasuaki; Hayami, Shinya; Horie, Yusuke; Okajima, Hajime; Sakamoto, Akira; Shiota, Yoshihito; Yoshizawa, Kazunari; Sato, Osamu; Journal of the American Chemical Society 141 (2019) 14384–14393; doi:10.1021/jacs.9b07204

data_4128801
_publ_section_title
;
 Observation of Proton Transfer Coupled Spin Transition and Trapping of
 Photoinduced Metastable Proton Transfer State in an Fe(II) Complex.
;
_journal_issue                   36
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14384
_journal_page_last               14393
_journal_paper_doi               10.1021/jacs.9b07204
_journal_volume                  141
_journal_year                    2019
_chemical_formula_moiety         'C38 H32 Fe N8 O4, 2(Cl O4)'
_chemical_formula_sum            'C38 H32 Cl2 Fe N8 O12'
_chemical_formula_weight         919.46
_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_creation_date             2018-05-29
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.18 svn.r3508 for OlexSys, GUI svn.r5497)
;
_cell_angle_alpha                90
_cell_angle_beta                 118.081(7)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   16.5756(9)
_cell_length_b                   15.8984(7)
_cell_length_c                   17.2953(10)
_cell_measurement_reflns_used    11271
_cell_measurement_temperature    300.15
_cell_measurement_theta_max      29.0910
_cell_measurement_theta_min      2.3320
_cell_volume                     4021.2(4)
_computing_cell_refinement       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_collection       'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_data_reduction        'CrysAlisPro 1.171.39.46b (Rigaku OD, 2018)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      300.15
_diffrn_detector                 'Rigaku HyPix-6000 area detector'
_diffrn_detector_area_resol_mean 10.0
_diffrn_detector_type            'HPC area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.868
_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    -39.00  78.00   0.50    8.54    --  -11.00  57.00-120.00  234
  2  \w    -38.00  71.00   0.50    8.54    --  -11.00  57.00 -60.00  218
  3  \w     40.00  72.00   0.50    8.54    --   11.80  57.00  30.00   64
  4  \w    -33.00  14.00   0.50    8.54    --   11.80 -82.00 -90.00   94
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'Rigaku XtaLAB Synergy-R'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0238138000
_diffrn_orient_matrix_UB_12      -0.0025937000
_diffrn_orient_matrix_UB_13      -0.0249236000
_diffrn_orient_matrix_UB_21      -0.0182610000
_diffrn_orient_matrix_UB_22      0.0395271000
_diffrn_orient_matrix_UB_23      -0.0193873000
_diffrn_orient_matrix_UB_31      0.0380784000
_diffrn_orient_matrix_UB_32      0.0204386000
_diffrn_orient_matrix_UB_33      0.0342047000
_diffrn_radiation_monochromator  'multi-layer mirror optics'
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0232
_diffrn_reflns_av_unetI/netI     0.0294
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.868
_diffrn_reflns_limit_h_max       23
_diffrn_reflns_limit_h_min       -21
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -22
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -21
_diffrn_reflns_number            35853
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.868
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         30.681
_diffrn_reflns_theta_min         2.339
_diffrn_source                   'rotating anode X-ray generator'
_diffrn_source_type              PhotonJet-R
_exptl_absorpt_coefficient_mu    0.582
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.55949
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.39.46b (Rigaku Oxford Diffraction, 2018)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    1.519
_exptl_crystal_description       plate
_exptl_crystal_F_000             1888
_exptl_crystal_size_max          0.866
_exptl_crystal_size_mid          0.135
_exptl_crystal_size_min          0.043
_refine_diff_density_max         0.330
_refine_diff_density_min         -0.378
_refine_diff_density_rms         0.042
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.055
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     634
_refine_ls_number_reflns         10813
_refine_ls_number_restraints     8
_refine_ls_restrained_S_all      1.058
_refine_ls_R_factor_all          0.0733
_refine_ls_R_factor_gt           0.0445
_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^)+(0.0624P)^2^+0.6207P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1173
_refine_ls_wR_factor_ref         0.1289
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7262
_reflns_number_total             10813
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja9b07204_si_006.cif
_cod_data_source_block           '[1OMe](ClO)_300K'
_cod_database_code               4128801
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C38 H32 Cl2 Fe N8 O12'
_reflns_odcompleteness_completeness 99.82
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     27.42
_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
 Cl2-O8 \\sim Cl2-O9
 with sigma of 0.02
 Cl2-O7 \\sim Cl2-O10
 with sigma of 0.02
 Cl2-O11 \\sim Cl2-O6
 with sigma of 0.02
 Cl2-O5 \\sim Cl2-O12
 with sigma of 0.02
 Cl1-O14 \\sim Cl1-O13
 with sigma of 0.02
 Cl1-O18 \\sim Cl1-O17
 with sigma of 0.02
 Cl1-O19 \\sim Cl1-O16
 with sigma of 0.02
 Cl1-O15 \\sim Cl1-O20
 with sigma of 0.02
3. Others
 Sof(O6)=Sof(O9)=Sof(O12)=Sof(O10)=1-FVAR(1)
 Sof(O8)=Sof(O7)=Sof(O11)=Sof(O5)=FVAR(1)
 Sof(O14)=Sof(O17)=Sof(O20)=Sof(O16)=1-FVAR(2)
 Sof(O18)=Sof(O19)=Sof(O15)=Sof(O13)=FVAR(2)
4.a Aromatic/amide H refined with riding coordinates:
 C32(H18), C14(H37), C1(H30), C35(H15), C19(H5), C2(H29), C22(H0AA), C4(H27),
 C15(H36), C33(H17), C3(H28), C17(H34), C34(H16), C20(H4), C16(H35), C21(H3A),
 C29(H11), C28(H10), C26(H8), C8(H21), C11(H24), C27(H9), C10(H23), C9(H22)
4.b Idealised Me refined as rotating group:
 C38(H19A,H19B,H19C), C37(H38A,H38B,H38C)
;
_shelx_res_checksum              70778
_shelx_hkl_checksum              41252
_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 1.494
_oxdiff_exptl_absorpt_empirical_full_min 0.466