Time-resolved EPR observation of blue-light-induced radical ion pairs in a flavin-Trp dyad.
Oka, Yoshimi; Inoue, Katsuya; Physical chemistry chemical physics : PCCP 26 (2024) 16444–16448; doi:10.1039/d3cp06219h

data_7248733
_publ_section_title
;
 Time-resolved EPR observation of blue-light-induced radical ion pairs in
 a flavin-Trp dyad.
;
_journal_issue                   23
_journal_name_full               'Physical chemistry chemical physics : PCCP'
_journal_page_first              16444
_journal_page_last               16448
_journal_paper_doi               10.1039/d3cp06219h
_journal_volume                  26
_journal_year                    2024
_chemical_absolute_configuration rmad
_chemical_formula_moiety         '3(C2 H6 O S), 0.5(H2 O), C31 H26 N6 O5'
_chemical_formula_sum            'C37 H45 N6 O8.5 S3'
_chemical_formula_weight         805.97
_chemical_name_common            (S)-Flavin-Trp(OMe)
_chemical_name_systematic
'(S)-2-Amino-N-(4-(7',8'-dimethylisoalloxazin-10'-yl)phenylcarbonyl)-3-(1H-indol-3-yl)propanoic acid methyl ester'
_space_group_crystal_system      triclinic
_space_group_IT_number           1
_space_group_name_Hall           'P 1'
_space_group_name_H-M_alt        'P 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     direct
_audit_creation_date             2024-03-14
_audit_creation_method
;
Olex2 1.3-ac4
(compiled 2020.11.27 svn.r5f609507 for Rigaku Oxford Diffraction, GUI svn.r6214)
;
_audit_update_record
;
2024-03-15 deposited with the CCDC.	2024-05-07 downloaded from the CCDC.
;
_cell_angle_alpha                72.4941(7)
_cell_angle_beta                 84.3059(8)
_cell_angle_gamma                81.3692(7)
_cell_formula_units_Z            2
_cell_length_a                   11.5061(2)
_cell_length_b                   13.0272(2)
_cell_length_c                   14.0938(2)
_cell_measurement_reflns_used    9860
_cell_measurement_temperature    173
_cell_measurement_theta_max      68.1665
_cell_measurement_theta_min      3.5865
_cell_volume                     1988.62(5)
_computing_cell_refinement       'SAINT V8.34A (Bruker AXS Inc., 2013)'
_computing_data_collection       'APEX2 (Bruker AXS, 2006)'
_computing_data_reduction        'SAINT V8.34A (Bruker AXS Inc., 2013)'
_computing_molecular_graphics    'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.3-ac4 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXS-1997  (Sheldrick, 2008)'
_diffrn_ambient_temperature      173
_diffrn_detector_area_resol_mean 8.3333
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.975
_diffrn_measurement_device_type  'Bruker APEXII Ultra CCD area detector'
_diffrn_measurement_method       'Phi and Omega scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0283
_diffrn_reflns_av_unetI/netI     0.0297
_diffrn_reflns_Laue_measured_fraction_full 0.979
_diffrn_reflns_Laue_measured_fraction_max 0.975
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -16
_diffrn_reflns_number            45924
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.975
_diffrn_reflns_theta_full        66.500
_diffrn_reflns_theta_max         68.283
_diffrn_reflns_theta_min         3.293
_diffrn_source                   'Bruker TXS fine-focus rotating anode'
_exptl_absorpt_coefficient_mu    2.201
_exptl_absorpt_correction_T_max  0.94
_exptl_absorpt_correction_T_min  0.83
_exptl_absorpt_correction_type   empirical
_exptl_absorpt_process_details   'SADABS (Sheldrick 1996)'
_exptl_crystal_colour            orange
_exptl_crystal_colour_primary    orange
_exptl_crystal_density_diffrn    1.346
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       plate
_exptl_crystal_F_000             850
_exptl_crystal_size_max          0.200
_exptl_crystal_size_mid          0.050
_exptl_crystal_size_min          0.030
_refine_diff_density_max         0.748
_refine_diff_density_min         -0.945
_refine_diff_density_rms         0.067
_refine_ls_abs_structure_details
;
 Flack x determined using 5205 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons, Flack and Wagner, Acta Cryst. B69 (2013) 249-259).
;
_refine_ls_abs_structure_Flack   0.067(7)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1141
_refine_ls_number_reflns         13619
_refine_ls_number_restraints     132
_refine_ls_restrained_S_all      1.046
_refine_ls_R_factor_all          0.0676
_refine_ls_R_factor_gt           0.0614
_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^)+(0.1114P)^2^+1.3384P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1713
_refine_ls_wR_factor_ref         0.1781
_reflns_Friedel_coverage         0.919
_reflns_Friedel_fraction_full    0.905
_reflns_Friedel_fraction_max     0.895
_reflns_number_gt                12256
_reflns_number_total             13619
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d3cp06219h2.cif
_cod_data_source_block           u140605mas1
_cod_depositor_comments          'Adding full bibliography for 7248733.cif.'
_cod_original_formula_sum        'C37 H45 N6 O8.50 S3'
_cod_database_code               7248733
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.937
_shelx_estimated_absorpt_t_min   0.667
_exptl_absorpt_special_details   'SADABS (Sheldrick 1996)'
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All N(H) groups
 At 1.5 times of:
  All C(H,H,H) groups, All S(H,H,H,H) groups
2. Restrained distances
 O17A-H17B
 0.98 with sigma of 0.02
 O17B-H17D
 0.98 with sigma of 0.02
 O17A-H17A
 0.98 with sigma of 0.02
 O17B-H17C
 0.98 with sigma of 0.02
 H17B-H17A
 1.55 with sigma of 0.04
 H17C-H17D
 1.55 with sigma of 0.04
3. Rigid bond restraints
 C67, S3, C68
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O14A, S4A, C69A, C70A
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 O14B, S4B, C69B, C70B
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
 O16A, S6A, C73A, C74A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O16B, S6B, C73B, C74B
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
4. Uiso/Uaniso restraints and constraints
C67 \\sim S3 \\sim C68: within 2A with sigma of 0.04 and sigma for terminal
atoms of 0.08 within 2A
O14A \\sim S4A \\sim C69A \\sim C70A: within 2A with sigma of 0.02 and sigma
for terminal atoms of 0.04 within 2A
O14B \\sim S4B \\sim C69B \\sim C70B: within 2A with sigma of 0.02 and sigma
for terminal atoms of 0.04 within 2A
O16A \\sim S6A \\sim C73A \\sim C74A: within 2A with sigma of 0.04 and sigma
for terminal atoms of 0.08 within 2A
O16B \\sim S6B \\sim C73B \\sim C74B: within 2A with sigma of 0.02 and sigma
for terminal atoms of 0.04 within 2A
5. Same fragment restrains
{S5A, O15A, C71A, C72A} sigma for 1-2: 0.02, 1-3: 0.04
as in
{S5B, O15B, C71B, C72B}
6. Others
 Sof(O13B)=1-FVAR(1)
 Sof(O13A)=FVAR(1)
 Sof(S4B)=Sof(O14B)=Sof(C69B)=Sof(H69D)=Sof(H69E)=Sof(H69F)=Sof(C70B)=
 Sof(H70D)=Sof(H70E)=Sof(H70F)=1-FVAR(2)
 Sof(S4A)=Sof(O14A)=Sof(C69A)=Sof(H69A)=Sof(H69B)=Sof(H69C)=Sof(C70A)=
 Sof(H70A)=Sof(H70B)=Sof(H70C)=FVAR(2)
 Sof(S5B)=Sof(O15B)=Sof(C71B)=Sof(H71D)=Sof(H71E)=Sof(H71F)=Sof(C72B)=
 Sof(H72D)=Sof(H72E)=Sof(H72F)=1-FVAR(3)
 Sof(S5A)=Sof(O15A)=Sof(C71A)=Sof(H71A)=Sof(H71B)=Sof(H71C)=Sof(C72A)=
 Sof(H72A)=Sof(H72B)=Sof(H72C)=FVAR(3)
 Sof(S6B)=Sof(O16B)=Sof(C73B)=Sof(H73D)=Sof(H73E)=Sof(H73F)=Sof(C74B)=
 Sof(H74D)=Sof(H74E)=Sof(H74F)=1-FVAR(4)
 Sof(S6A)=Sof(O16A)=Sof(C73A)=Sof(H73A)=Sof(H73B)=Sof(H73C)=Sof(C74A)=
 Sof(H74A)=Sof(H74B)=Sof(H74C)=FVAR(4)
 Sof(O17B)=Sof(H17C)=Sof(H17D)=1-FVAR(5)
 Sof(O17A)=Sof(H17A)=Sof(H17B)=FVAR(5)
7.a Ternary CH refined with riding coordinates:
 C1(H1), C32(H32)
7.b Secondary CH2 refined with riding coordinates:
 C21(H21A,H21B), C52(H52A,H52B)
7.c Me refined with riding coordinates:
 C71A(H71A,H71B,H71C), C72A(H72A,H72B,H72C), C71B(H71D,H71E,H71F), C72B(H72D,
 H72E,H72F), C73A(H73A,H73B,H73C), C74A(H74A,H74B,H74C), C73B(H73D,H73E,H73F),
 C74B(H74D,H74E,H74F)
7.d Aromatic/amide H refined with riding coordinates:
 C4(H4), C5(H5), C7(H7), C8(H8), C14(H14), C17(H17), C23(H23), C25(H25),
 C26(H26), C27(H27), C28(H28), C35(H35), C36(H36), C38(H38), C39(H39), C45(H45),
  C48(H48), C54(H54), C56(H56), C57(H57), C58(H58), C59(H59), N1(H1A), N4(H4A),
 N6(H6), N7(H7A), N10(H10), N12(H12)
7.e Idealised Me refined as rotating group:
 C69A(H69A,H69B,H69C), C70A(H70A,H70B,H70C), C69B(H69D,H69E,H69F), C70B(H70D,
 H70E,H70F), C19(H19A,H19B,H19C), C20(H20A,H20B,H20C), C31(H31A,H31B,H31C),
 C50(H50A,H50B,H50C), C51(H51A,H51B,H51C), C62(H62A,H62B,H62C), C63(H63A,H63B,
 H63C), C64(H64A,H64B,H64C), C65(H65A,H65B,H65C), C66(H66A,H66B,H66C), C67(H67A,
 H67B,H67C), C68(H68A,H68B,H68C)
;
_olex2_submission_special_instructions 'No special instructions were received'