Kinetics of Multielectron Transfers and Redox-Induced Structural Changes in N-Aryl-Expanded Pyridiniums: Establishing Their Unusual, Versatile Electrophoric Activity.
Lachmanová, Štěpánka; Dupeyre, Grégory; Tarábek, Ján; Ochsenbein, Philippe; Perruchot, Christian; Ciofini, Ilaria; Hromadová, Magdaléna; Pospíšil, Lubomír; Lainé, Philippe P; Journal of the American Chemical Society 137 (2015) 11349–11364; doi:10.1021/jacs.5b05545

data_4124311
_publ_section_title
;
 Kinetics of Multielectron Transfers and Redox-Induced Structural Changes
 in N-Aryl-Expanded Pyridiniums: Establishing Their Unusual, Versatile
 Electrophoric Activity.
;
_journal_issue                   35
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              11349
_journal_page_last               11364
_journal_paper_doi               10.1021/jacs.5b05545
_journal_volume                  137
_journal_year                    2015
_chemical_compound_source        'see text'
_chemical_formula_moiety         '(C40 H29 N2) (B F4) (C H2 Cl2)'
_chemical_formula_sum            'C41 H31 B Cl2 F4 N2'
_chemical_formula_weight         709.39
_chemical_name_common            Laine_Dyad_2014
_chemical_name_systematic        '[Py(ph)2-TP+](BF4)'
_space_group_crystal_system      orthorhombic
_space_group_IT_number           19
_space_group_name_Hall           'P 2ac 2ab'
_space_group_name_H-M_alt        'P 21 21 21'
_symmetry_space_group_name_Hall  'P 2ac 2ab'
_symmetry_space_group_name_H-M   'P 21 21 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_atom_sites_solution_secondary   difmap
_audit_creation_date             'Jun 15 11:19:06 2014'
_audit_creation_method           'APEX2 v2011.8-0'
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   9.7854(2)
_cell_length_b                   15.4462(3)
_cell_length_c                   22.2111(4)
_cell_measurement_reflns_used    9916
_cell_measurement_temperature    113(2)
_cell_measurement_theta_max      60.2112
_cell_measurement_theta_min      4.8947
_cell_volume                     3357.15(11)
_computing_cell_refinement       'APEX2 v2011.8-0 (Bruker AXS)'
_computing_data_collection       'Bruker Instrument Service v2011.8.1.0'
_computing_data_reduction        'APEX2 v2011.8-0 (Bruker AXS)'
_computing_publication_material  'PLATON (Spek, 2003)'
_computing_structure_refinement  'SHELXL-97 (Sheldrick, 1997)'
_computing_structure_solution    'SHELXS-97 (Sheldrick, 1990)'
_diffrn_ambient_temperature      113(1)
_diffrn_measured_fraction_theta_full 0.959
_diffrn_measured_fraction_theta_max 0.963
_diffrn_measurement_device_type  'Bruker Instrument Service v2011.8.1.0'
_diffrn_measurement_method       '\p and \w scan'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0286
_diffrn_reflns_av_unetI/netI     0.0286
_diffrn_reflns_Laue_measured_fraction_full 0.959
_diffrn_reflns_Laue_measured_fraction_max 0.963
_diffrn_reflns_limit_h_max       9
_diffrn_reflns_limit_h_min       -10
_diffrn_reflns_limit_k_max       18
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       26
_diffrn_reflns_limit_l_min       -26
_diffrn_reflns_number            26231
_diffrn_reflns_point_group_measured_fraction_full 0.934
_diffrn_reflns_point_group_measured_fraction_max 0.938
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         67.439
_diffrn_reflns_theta_min         4.904
_diffrn_source                   'micro source'
_exptl_absorpt_coefficient_mu    2.212
_exptl_absorpt_correction_T_max  0.7530
_exptl_absorpt_correction_T_min  0.5929
_exptl_absorpt_correction_type   analytical
_exptl_absorpt_process_details   'SADABS V2008/1 (Bruker AXS)'
_exptl_crystal_colour            'pale pink'
_exptl_crystal_density_diffrn    1.404
_exptl_crystal_description       plate
_exptl_crystal_F_000             1464
_exptl_crystal_size_max          0.18
_exptl_crystal_size_mid          0.14
_exptl_crystal_size_min          0.06
_refine_diff_density_max         0.532
_refine_diff_density_min         -0.689
_refine_diff_density_rms         0.109
_refine_ls_abs_structure_details
;
 Flack x determined using 2325 quotients [(I+)-(I-)]/[(I+)+(I-)]
 (Parsons and Flack (2004), Acta Cryst. A60, s61).
;
_refine_ls_abs_structure_Flack   0.070(4)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   2.100
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     451
_refine_ls_number_reflns         5670
_refine_ls_number_restraints     2
_refine_ls_restrained_S_all      2.101
_refine_ls_R_factor_all          0.0556
_refine_ls_R_factor_gt           0.0551
_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^)+(0.0800P)^2^]
 where P=(Fo^2^+2Fc^2^)/3
;
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1854
_refine_ls_wR_factor_ref         0.1862
_reflns_Friedel_coverage         0.727
_reflns_Friedel_fraction_full    0.902
_reflns_Friedel_fraction_max     0.905
_reflns_number_gt                5594
_reflns_number_total             5670
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b05545_si_002.cif
_cod_data_source_block           Laine2014PyPh2TP
_cod_depositor_comments          'Adding full bibliography for 4124311.cif.'
_cod_database_code               4124311
_shelxl_version_number           2013-2
_shelx_res_checksum              5277
_shelx_hkl_checksum              19024