Probing Distance Dependent Charge-Transfer Character in Excimers of Extended Viologen Cyclophanes Using Femtosecond Vibrational Spectroscopy.
Wu, Yilei; Zhou, Jiawang; Phelan, Brian T.; Mauck, Catherine M.; Stoddart, J. Fraser; Young, Ryan M.; Wasielewski, Michael R.; Journal of the American Chemical Society 139 (2017) 14265–14276; doi:10.1021/jacs.7b08275

data_4131661
_publ_section_title
;
 Probing Distance Dependent Charge-Transfer Character in Excimers of
 Extended Viologen Cyclophanes Using Femtosecond Vibrational Spectroscopy.
;
_journal_issue                   40
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              14265
_journal_page_last               14276
_journal_paper_doi               10.1021/jacs.7b08275
_journal_volume                  139
_journal_year                    2017
_chemical_formula_moiety         'C48 H40 N4, 4(F6 P), 6(C2 H3 N)'
_chemical_formula_sum            'C60 H58 F24 N10 P4'
_chemical_formula_weight         1499.04
_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   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2016-06-09
_audit_creation_method
;
Olex2 1.2
(compiled 2016.02.19 svn.r3266 for OlexSys, GUI svn.r5155)
;
_cell_angle_alpha                88.7203(15)
_cell_angle_beta                 89.3061(17)
_cell_angle_gamma                88.8464(16)
_cell_formula_units_Z            1
_cell_length_a                   7.3123(2)
_cell_length_b                   12.9010(3)
_cell_length_c                   19.3466(5)
_cell_measurement_reflns_used    6829
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      65.075
_cell_measurement_theta_min      3.428
_cell_volume                     1824.13(8)
_computing_cell_refinement       'SAINT V8.34A (Bruker, 2013)'
_computing_data_collection       'APEX2 V2014.11-0 (Bruker, 2014)'
_computing_data_reduction        'Bruker SAINT'
_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      99.93
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.900
_diffrn_measured_fraction_theta_max 0.954
_diffrn_measurement_device_type  'Bruker Kappa APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  'Quazar optics'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0257
_diffrn_reflns_av_unetI/netI     0.0329
_diffrn_reflns_Laue_measured_fraction_full 0.900
_diffrn_reflns_Laue_measured_fraction_max 0.954
_diffrn_reflns_limit_h_max       8
_diffrn_reflns_limit_h_min       -8
_diffrn_reflns_limit_k_max       11
_diffrn_reflns_limit_k_min       -15
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            12124
_diffrn_reflns_point_group_measured_fraction_full 0.900
_diffrn_reflns_point_group_measured_fraction_max 0.954
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         65.070
_diffrn_reflns_theta_min         2.284
_diffrn_source                   microsource
_exptl_absorpt_coefficient_mu    1.899
_exptl_absorpt_correction_T_max  0.7526
_exptl_absorpt_correction_T_min  0.6659
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/5 (Bruker,2014/5) was used for absorption correction.
wR2(int) was 0.0511 before and 0.0344 after correction.
The Ratio of minimum to maximum transmission is 0.8848.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.365
_exptl_crystal_description       platelet
_exptl_crystal_F_000             764
_exptl_crystal_size_max          0.19
_exptl_crystal_size_mid          0.088
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.403
_refine_diff_density_min         -0.323
_refine_diff_density_rms         0.054
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.056
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     571
_refine_ls_number_reflns         5944
_refine_ls_number_restraints     208
_refine_ls_restrained_S_all      1.237
_refine_ls_R_factor_all          0.0642
_refine_ls_R_factor_gt           0.0534
_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^)+(0.0661P)^2^+1.6193P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1356
_refine_ls_wR_factor_ref         0.1415
_reflns_Friedel_coverage         0.000
_reflns_number_gt                4888
_reflns_number_total             5944
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja7b08275_si_003.cif
_cod_data_source_block           cx0783
_cod_database_code               4131661
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.928
_shelx_estimated_absorpt_t_min   0.714
_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
 P1-F5 \\sim P1-F4A \\sim P1-F4 \\sim P1-F3A \\sim P1-F3 \\sim P1-F6A \\sim
P1-F6 \\sim P1-F5A \\sim P2A-F7A ~
 P2A-F11A \\sim P2-F7 \\sim P2-F11 \\sim P2A-F12A \\sim P2A-F8A \\sim P2A-F9A
\\sim P2-F12 \\sim P2-F9 \\sim P2-
 F10 \\sim P2A-F10A \\sim P2-F8
 with sigma of 0.01
3. Rigid body (RIGU) restrains
 F8A, F7A, F10A, F9A, F12A, F11A, F12, F8, F7, F11, F10, F9, C29, N5, C30,
 C29A, N5A, C30A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 Sof(F3A)=Sof(F4A)=Sof(F5A)=Sof(F6A)=1-FVAR(1)
 Sof(F3)=Sof(F4)=Sof(F5)=Sof(F6)=FVAR(1)
 Sof(P2A)=Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(F10A)=Sof(F11A)=Sof(F12A)=1-FVAR(2)
 Sof(P2)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(F10)=Sof(F11)=Sof(F12)=FVAR(2)
 Sof(N5A)=Sof(C29A)=Sof(C30A)=Sof(H30A)=Sof(H30B)=Sof(H30C)=1-FVAR(3)
 Sof(C29)=Sof(N5)=Sof(C30)=Sof(H30D)=Sof(H30E)=Sof(H30F)=FVAR(3)
5.a Secondary CH2 refined with riding coordinates:
 C1(H1A,H1B), C18(H18A,H18B)
5.b Me refined with riding coordinates:
 C28(H28A,H28B,H28C), C26(H26A,H26B,H26C), C30A(H30A,H30B,H30C), C30(H30D,H30E,
 H30F)
5.c Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C5(H5), C6(H6), C8(H8), C9(H9), C11(H11), C12(H12), C14(H14),
 C15(H15), C16(H16), C17(H17), C21(H21), C22(H22), C23(H23), C24(H24)
;
_smtbx_masks_special_details
;
The solvent masking procedure as implemented in Olex2 was used to remove the
electronic contribution of solvent molecules from the refinement.  As the exact
solvent content is not known, only the atoms used in the refinement model are
reported in the formula here.

Total solvent accessible volume / cell = 239.5 Ang^3^ [13.1%]
Total electron count / cell = 64.6
;
_shelx_res_checksum              97347
_shelx_hkl_checksum              40160
_olex2_date_sample_data_collection 2016-06-08
_olex2_date_sample_submission    2016-06-03
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a MITIGEN holder in Paratone oil'
_olex2_submission_original_sample_id cx0783
_olex2_submission_special_instructions 'No special instructions were received'