Energy and Electron Transfer Dynamics within a Series of Perylene Diimide/Cyclophane Systems.
Ryan, Seán T J; Young, Ryan M.; Henkelis, James J.; Hafezi, Nema; Vermeulen, Nicolaas A.; Hennig, Andreas; Dale, Edward J.; Wu, Yilei; Krzyaniak, Matthew D.; Fox, Athan; Nau, Werner M.; Wasielewski, Michael R.; Stoddart, J. Fraser; Scherman, Oren A.; Journal of the American Chemical Society 137 (2015) 15299–15307; doi:10.1021/jacs.5b10329

data_4129752
_publ_section_title
;
 Energy and Electron Transfer Dynamics within a Series of Perylene
 Diimide/Cyclophane Systems.
;
_journal_issue                   48
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              15299
_journal_page_last               15307
_journal_paper_doi               10.1021/jacs.5b10329
_journal_volume                  137
_journal_year                    2015
_chemical_formula_moiety
'2(C50 H56 N4 O10), 2(C44 H36 N4 Se2), 12(F6 P), 7(C2 H3 N)'
_chemical_formula_sum            'C202 H205 F72 N23 O20 P12 Se4'
_chemical_formula_weight         5330.36
_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     dual
_audit_creation_date             2015-02-09
_audit_creation_method
;
Olex2 1.2
(compiled 2015.01.26 svn.r3151 for OlexSys, GUI svn.r4998)
;
_cell_angle_alpha                93.428(3)
_cell_angle_beta                 102.052(3)
_cell_angle_gamma                107.203(2)
_cell_formula_units_Z            2
_cell_length_a                   16.2898(8)
_cell_length_b                   24.1007(13)
_cell_length_c                   32.3023(17)
_cell_measurement_reflns_used    9707
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      24.537
_cell_measurement_theta_min      2.836
_cell_volume                     11746.7(11)
_computing_cell_refinement       'SAINT V7.23A (Bruker, 2005)'
_computing_data_collection       'APEX2 V2.1-4 (Bruker, 2007)'
_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, 2008)'
_computing_structure_solution    'ShelXD (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.07
_diffrn_detector_area_resol_mean 8
_diffrn_measured_fraction_theta_full 0.867
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker SMART APEX CCD area detector'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0380
_diffrn_reflns_av_unetI/netI     0.0497
_diffrn_reflns_Laue_measured_fraction_full 0.867
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       19
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       27
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            150767
_diffrn_reflns_point_group_measured_fraction_full 0.867
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        26.000
_diffrn_reflns_theta_max         24.768
_diffrn_reflns_theta_min         1.170
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    0.828
_exptl_absorpt_correction_T_max  0.7451
_exptl_absorpt_correction_T_min  0.6790
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0497 before and 0.0439 after correction.
The Ratio of minimum to maximum transmission is 0.9113.
The \l/2 correction factor is 0.0015.
;
_exptl_crystal_colour            pink
_exptl_crystal_colour_primary    pink
_exptl_crystal_density_diffrn    1.507
_exptl_crystal_description       Block
_exptl_crystal_F_000             5404
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.2
_exptl_crystal_size_min          0.2
_refine_diff_density_max         1.637
_refine_diff_density_min         -1.055
_refine_diff_density_rms         0.163
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.113
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     3364
_refine_ls_number_reflns         40034
_refine_ls_number_restraints     4303
_refine_ls_restrained_S_all      1.155
_refine_ls_R_factor_all          0.1202
_refine_ls_R_factor_gt           0.0868
_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^)+(0.1910P)^2^+10.2970P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2637
_refine_ls_wR_factor_ref         0.2878
_reflns_Friedel_coverage         0.000
_reflns_number_gt                27788
_reflns_number_total             40034
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja5b10329_si_003.cif
_cod_data_source_block           final
_cod_database_code               4129752
_shelxl_version_number           2013-4
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 Se4B-C73B \\sim Se4A-C73A \\sim Se4B-C74B \\sim Se4A-C74A
 with sigma of 0.02
 Se4B-C75B \\sim Se4B-C72B \\sim Se4A-C72A \\sim Se4A-C75A
 with sigma of 0.02
 C73B-C72B \\sim C73B-C74B \\sim C75B-C74B \\sim C75A-C74A \\sim C73A-C74A
\\sim C73A-C72A
 with sigma of 0.02
 C69-C72B \\sim C69-C72A \\sim C75A-C76 \\sim C75B-C76
 with sigma of 0.02
3. Restrained angles
 F64B-P11B-F62B
 fixed at 90 with sigma of 0.02
 F63B-P11B-F64B
 fixed at 90 with sigma of 0.02
4. Restrained planarity
 Se4B, C72B, C73B, C74B, C75B
 with sigma of 0.1
5. Rigid bond restraints
 All non-hydrogen atoms
 with sigma for 1-2 distances of 0.1 and sigma for 1-3 distances of 0.01
6. Uiso/Uaniso restraints and constraints
All non-hydrogen atoms have similar U: within 2A with sigma of 0.1 and sigma
for terminal atoms of 0.01
Uanis(C72B) \\sim Ueq, Uanis(C74B) \\sim Ueq, Uanis(C73B) \\sim Ueq,
Uanis(C75B) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.001
Uanis(C129) \\sim Ueq, Uanis(C130) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.001
Uanis(C173) \\sim Ueq, Uanis(C174) \\sim Ueq, Uanis(C175) \\sim Ueq,
Uanis(C176) \\sim Ueq, Uanis(C177) \\sim Ueq, Uanis(C178) \\sim Ueq, Uanis(O18)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.001
Uanis(C122) = Uanis(C121) = Uanis(C121) = Uanis(O6B) = Uanis(O6A)
Uanis(O7) = Uanis(C122) = Uanis(C122) = Uanis(C121) = Uanis(C121) = Uanis(O6B)
= Uanis(O6A)
Uanis(C123) = Uanis(C124) = Uanis(C125) = Uanis(C127) = Uanis(C126) =
Uanis(C128)
7. Same fragment restrains
{P5, F30, F29, F25, F27, F28, F26} sigma for 1-2: 0.02, 1-3: 0.02
as
{P13B, F73B, F74B, F75B, F76B, F77B, F78B}
{P12A, F68A, F69A, F67A, F70A, F71A, F72A} sigma for 1-2: 0.02, 1-3: 0.02
as
{P12B, F67B, F68B, F69B, F70B, F71B, F72B}
{P5, F27, F28, F26, F25, F29, F30} sigma for 1-2: 0.02, 1-3: 0.02
as
{P13A, F73A, F74A, F75A, F76A, F77A, F78A}
{P11B, F66B, F62B, F65B, F63B, F61B, F64B} sigma for 1-2: 0.02, 1-3: 0.02
as
{P11A, F61A, F62A, F63A, F64A, F65A, F66A}
8. Others
 Sof(Se4B)=Sof(C72B)=Sof(C73B)=Sof(H73B)=Sof(C74B)=Sof(H74B)=Sof(C75B)=1-FVAR(1)
 Sof(Se4A)=Sof(C72A)=Sof(C73A)=Sof(H73A)=Sof(C74A)=Sof(H74A)=Sof(C75A)=FVAR(1)
 Sof(P12B)=Sof(F67B)=Sof(F68B)=Sof(F69B)=Sof(F70B)=Sof(F71B)=Sof(F72B)=1-FVAR(2)
 Sof(P12A)=Sof(F68A)=Sof(F69A)=Sof(F67A)=Sof(F70A)=Sof(F71A)=Sof(F72A)=FVAR(2)
 Sof(O17B)=Sof(H17G)=Sof(H17H)=1-FVAR(3)
 Sof(O17A)=Sof(H17E)=Sof(H17F)=FVAR(3)
 Sof(P13A)=Sof(F73A)=Sof(F74A)=Sof(F75A)=Sof(F76A)=Sof(F77A)=Sof(F78A)=1-FVAR(4)
 Sof(P13B)=Sof(F73B)=Sof(F74B)=Sof(F75B)=Sof(F76B)=Sof(F77B)=Sof(F78B)=FVAR(4)
 Sof(O6B)=Sof(H12C)=Sof(H12D)=1-FVAR(5)
 Sof(O6A)=Sof(H12A)=Sof(H12B)=FVAR(5)
 Sof(C221)=Sof(H22A)=Sof(H22B)=1-FVAR(6)
 Sof(C121)=Sof(H12E)=Sof(H12F)=FVAR(6)
 Sof(C222)=Sof(H22C)=Sof(H22D)=1-FVAR(7)
 Sof(C122)=Sof(H12G)=Sof(H12H)=FVAR(7)
 Sof(P10B)=Sof(F55B)=Sof(F56B)=Sof(F57B)=Sof(F58B)=Sof(F59B)=Sof(F60B)=1-FVAR(8)
 Sof(P10A)=Sof(F55A)=Sof(F56A)=Sof(F57A)=Sof(F58A)=Sof(F59A)=Sof(F60A)=FVAR(8)
 Sof(P11A)=Sof(F61A)=Sof(F62A)=Sof(F63A)=Sof(F64A)=Sof(F65A)=Sof(F66A)=1-FVAR(9)
 Sof(P11B)=Sof(F66B)=Sof(F62B)=Sof(F65B)=Sof(F63B)=Sof(F61B)=Sof(F64B)=FVAR(9)
 Fixed Sof: P2(0.69) F1B(0.69) F7(0.69) F9(0.69) F11(0.69) F12(0.69) F19(0.69)
 P4(0.31) F21(0.31) F23(0.31) F20(0.31) F24(0.31) F1F(0.31) F22(0.31)
9.a Secondary CH2 refined with riding coordinates:
 C113(H11A,H11B), C114(H11C,H11D), C117(H11K,H11L), C118(H11M,H11N), C119(H11O,
 H11P), C120(H12A,H12B), C120(H12C,H12D), C121(H12E,H12F), C122(H12G,H12H),
 C123(H12I,H12J), C128(H12K,H12L), C129(H12M,H12N), C130(H13A,H13B), C131(H13C,
 H13D), C132(H13E,H13F), C133(H13G,H13H), C134(H13I,H13J), C137(H13Q,H13R),
 C138(H13S,H13T), C221(H22A,H22B), C222(H22C,H22D), C59(H59A,H59B), C66(H66A,
 H66B), C81(H81A,H81B), C88(H88A,H88B), C163(H16A,H16B), C164(H16C,H16D),
 C167(H16K,H16L), C168(H16M,H16N), C169(H16O,H16P), C170(H17A,H17B), C171(H17C,
 H17D), C172(H17E,H17F), C172(H17G,H17H), C173(H17I,H17J), C178(H17K,H17L),
 C179(H17M,H17N), C180(H18A,H18B), C181(H18C,H18D), C182(H18E,H18F), C183(H18G,
 H18H), C184(H18I,H18J), C187(H18Q,H18R), C188(H18S,H18T), C15(H15A,H15B),
 C22(H22E,H22F), C37(H37A,H37B), C44(H44A,H44B)
9.b Aromatic/amide H refined with riding coordinates:
 C94(H94), C95(H95), C99(H99), C100(H100), C104(H104), C105(H105), C109(H109),
 C110(H110), C45(H45), C46(H46), C48(H48), C49(H49), C51(H51), C52(H52),
 C55(H55), C56(H56), C57(H57), C58(H58), C61(H61), C62(H62), C64(H64), C65(H65),
  C67(H67), C68(H68), C70(H70), C71(H71), C73B(H73B), C73A(H73A), C74A(H74A),
 C74B(H74B), C77(H77), C78(H78), C79(H79), C80(H80), C83(H83), C84(H84),
 C86(H86), C87(H87), C144(H144), C145(H145), C149(H149), C150(H150), C154(H154),
  C155(H155), C159(H159), C160(H160), C1(H1), C2(H2), C4(H4), C5(H5), C7(H7),
 C8(H8), C11(H11), C12(H12), C13(H13), C14(H14), C17(H17), C18(H18), C20(H20),
 C21(H21), C23(H23), C24(H24), C26(H26), C27(H27), C29(H29), C30(H30), C33(H33),
  C34(H34), C35(H35), C36(H36), C39(H39), C40(H40), C42(H42), C43(H43)
9.c Idealised Me refined as rotating group:
 C115(H11E,H11F,H11G), C116(H11H,H11I,H11J), C135(H13K,H13L,H13M), C136(H13N,
 H13O,H13P), C165(H16E,H16F,H16G), C166(H16H,H16I,H16J), C185(H18K,H18L,H18M),
 C186(H18N,H18O,H18P), C1S(H1SA,H1SB,H1SC), C9S(H9SA,H9SB,H9SC), C13S(H13U,H13V,
 H13W), C3S(H3SA,H3SB,H3SC), C11S(H11Q,H11R,H11S), C5S(H5SA,H5SB,H5SC),
 C7S(H7SA,H7SB,H7SC)
;
_smtbx_masks_special_details
;
The solvent masking procedure as implemented in Olex2 was used to remove the
electronic contribution of masked solvent and PF6 counterion molecules from
the refinement. Only the atoms used in the refinement are reported in the
formula here.

Total solvent accessible volume / cell = 879.0 Ang^3 [7.5%]
Total electron count / cell = 279.7
;