Covalent Radical Pairs as Spin Qubits: Influence of Rapid Electron Motion between Two Equivalent Sites on Spin Coherence.
Wu, Yilei; Zhou, Jiawang; Nelson, Jordan N.; Young, Ryan M.; Krzyaniak, Matthew D.; Wasielewski, Michael R.; Journal of the American Chemical Society 140 (2018) 13011–13021; doi:10.1021/jacs.8b08105

data_4133042
_publ_section_title
;
 Covalent Radical Pairs as Spin Qubits: Influence of Rapid Electron Motion
 between Two Equivalent Sites on Spin Coherence.
;
_journal_issue                   40
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              13011
_journal_page_last               13021
_journal_paper_doi               10.1021/jacs.8b08105
_journal_volume                  140
_journal_year                    2018
_chemical_formula_moiety         'C50 H44 N4 O2, 4(F6 P), 0.25(O)'
_chemical_formula_sum            'C50 H44 F24 N4 O2.25 P4'
_chemical_formula_weight         1316.77
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2017-09-15
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                103.786(3)
_cell_angle_beta                 103.714(3)
_cell_angle_gamma                91.567(3)
_cell_formula_units_Z            1
_cell_length_a                   8.4372(4)
_cell_length_b                   9.7417(5)
_cell_length_c                   17.5976(8)
_cell_measurement_reflns_used    7047
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      63.779
_cell_measurement_theta_min      2.671
_cell_volume                     1359.28(12)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_collection       'APEX2 V2014.11-0 (Bruker, 2014)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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      100.0
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'MX optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0360
_diffrn_reflns_av_unetI/netI     0.0367
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       8
_diffrn_reflns_limit_k_min       -11
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            13555
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        63.843
_diffrn_reflns_theta_max         63.843
_diffrn_reflns_theta_min         2.671
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    2.455
_exptl_absorpt_correction_T_max  0.7524
_exptl_absorpt_correction_T_min  0.6627
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1031 before and 0.0461 after correction. The Ratio of minimum to maximum transmission is 0.8808. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.609
_exptl_crystal_description       plate
_exptl_crystal_F_000             666
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by as supplied'
_exptl_crystal_size_max          0.233
_exptl_crystal_size_mid          0.114
_exptl_crystal_size_min          0.016
_refine_diff_density_max         0.689
_refine_diff_density_min         -0.368
_refine_diff_density_rms         0.088
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.027
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     531
_refine_ls_number_reflns         4428
_refine_ls_number_restraints     561
_refine_ls_restrained_S_all      1.275
_refine_ls_R_factor_all          0.0804
_refine_ls_R_factor_gt           0.0675
_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^)+(0.1127P)^2^+2.6038P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1869
_refine_ls_wR_factor_ref         0.1989
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3588
_reflns_number_total             4428
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja8b08105_si_002.cif
_cod_data_source_block           cx1065
_cod_database_code               4133042
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.962
_shelx_estimated_absorpt_t_min   0.599
_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
 O2A-C12A = O2-C12 = O2-C14 = O2A-C14A = O1-C9 = O1A-C9A = O1A-C13A = O1-C13
 1.4 with sigma of 0.02
 C16-C15 \\sim C16-H16 \\sim C16-C17
 with sigma of 0.01
3. Rigid bond restraints
 O1, O1A, O2, O2A, C13, C13A, C14, C14A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
O1 \\sim O1A \\sim O2 \\sim O2A \\sim C13 \\sim C13A \\sim C14 \\sim C14A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C13A) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Others
 Sof(C2A)=Sof(H2A)=Sof(C3A)=Sof(H3A)=Sof(C5A)=Sof(H5A)=Sof(C6A)=Sof(H6A)=1-
 FVAR(1)
 Sof(C2)=Sof(H2)=Sof(C3)=Sof(H3)=Sof(C5)=Sof(H5)=Sof(C6)=Sof(H6)=FVAR(1)
 Sof(C10A)=Sof(C9A)=Sof(C8A)=Sof(H8A)=Sof(C7A)=Sof(C12A)=Sof(C11A)=Sof(H11A)=1-
 FVAR(2)
 Sof(O1A)=Sof(O2A)=Sof(H9)=Sof(H12)=Sof(C13A)=Sof(H13D)=Sof(H13E)=Sof(H13F)=
 Sof(C14A)=Sof(H14D)=Sof(H14E)=Sof(H14F)=0.5*(1-FVAR(3))
 Sof(O1)=Sof(O2)=Sof(H9A)=Sof(H12A)=Sof(C13)=Sof(H13A)=Sof(H13B)=Sof(H13C)=
 Sof(C14)=Sof(H14A)=Sof(H14B)=Sof(H14C)=0.5*FVAR(3)
 Sof(C7)=Sof(C8)=Sof(H8)=Sof(C9)=Sof(C10)=Sof(C12)=Sof(C11)=Sof(H11)=FVAR(2)
 Fixed Sof: O1S(0.125)
 Fixed Y: O1S(0)
 Fixed Z: O1S(0.5)
7.a Everything fixed:
 H9, H9A, H8A, H12A, H12, O1S
7.b Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C20(H20A,H20B)
7.c Me refined with riding coordinates:
 C14A(H14D,H14E,H14F)
7.d Aromatic/amide H refined with riding coordinates:
 C2(H2), C2A(H2A), C3(H3), C3A(H3A), C5(H5), C5A(H5A), C6(H6), C6A(H6A),
 C8(H8), C11(H11), C16(H16), C17(H17), C18(H18), C19(H19), C22(H22), C24(H24),
 C25(H25), C26(H26)
7.e Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C13A(H13D,H13E,H13F), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              86343
_shelx_hkl_checksum              34642
_olex2_date_sample_data_collection 2017-09-14
_olex2_date_sample_submission    2017-09-12
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a glass fibre in Paratone oil'
_olex2_submission_original_sample_id cx1065
_olex2_submission_special_instructions 'No special instructions were received'