Conjugated Oligomers with Stable Radical Substituents: Synthesis, Single Crystal Structures, Electronic Structure, and Excited State Dynamics
Huang, Yiming; Xu, Zihao; Jin, Shijian; Li, Chenyang; Warncke, Kurt; Evangelista, Francesco A.; Lian, Tianquan; Egap, Eilaf; Chemistry of Materials 30 (2018) 7840–; doi:10.1021/acs.chemmater.8b03366

data_4003385
_publ_section_title
;
 Conjugated Oligomers with Stable Radical Substituents: Synthesis, Single
 Crystal Structures, Electronic Structure, and Excited State Dynamics
;
_journal_issue                   21
_journal_name_full               'Chemistry of Materials'
_journal_page_first              7840
_journal_paper_doi               10.1021/acs.chemmater.8b03366
_journal_volume                  30
_journal_year                    2018
_chemical_formula_moiety         'C66 H86.96 N4 O4 S4'
_chemical_formula_sum            'C66 H86.96 N4 O4 S4'
_chemical_formula_weight         1128.60
_space_group_crystal_system      trigonal
_space_group_IT_number           148
_space_group_name_Hall           '-R 3'
_space_group_name_H-M_alt        'R -3 :H'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2016-09-21
_audit_creation_method
;
Olex2 1.2-alpha
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                120
_cell_formula_units_Z            18
_cell_length_a                   81.554(3)
_cell_length_b                   81.554(3)
_cell_length_c                   7.1811(3)
_cell_measurement_reflns_used    9861
_cell_measurement_temperature    100(2)
_cell_measurement_theta_max      64.69
_cell_measurement_theta_min      2.87
_cell_volume                     41363(3)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL (Sheldrick, 2008)'
_diffrn_ambient_temperature      100.15
_diffrn_measured_fraction_theta_full 0.978
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0820
_diffrn_reflns_av_unetI/netI     0.0627
_diffrn_reflns_Laue_measured_fraction_full 0.978
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       95
_diffrn_reflns_limit_h_min       -73
_diffrn_reflns_limit_k_max       95
_diffrn_reflns_limit_k_min       -95
_diffrn_reflns_limit_l_max       8
_diffrn_reflns_limit_l_min       -7
_diffrn_reflns_number            99380
_diffrn_reflns_point_group_measured_fraction_full 0.978
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        65.081
_diffrn_reflns_theta_max         65.081
_diffrn_reflns_theta_min         2.867
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.209
_exptl_absorpt_correction_T_max  0.7526
_exptl_absorpt_correction_T_min  0.6602
_exptl_absorpt_correction_type   none
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1229 before and 0.0722 after correction.
The Ratio of minimum to maximum transmission is 0.8772.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            green
_exptl_crystal_colour_primary    green
_exptl_crystal_density_diffrn    0.816
_exptl_crystal_description       needle
_exptl_crystal_F_000             10925
_exptl_crystal_size_max          0.313
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.058
_refine_diff_density_max         1.428
_refine_diff_density_min         -0.796
_refine_diff_density_rms         0.144
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.524
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     727
_refine_ls_number_reflns         15354
_refine_ls_number_restraints     388
_refine_ls_restrained_S_all      1.555
_refine_ls_R_factor_all          0.1855
_refine_ls_R_factor_gt           0.1385
_refine_ls_shift/su_max          5.405
_refine_ls_shift/su_mean         0.063
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3827
_refine_ls_wR_factor_ref         0.4171
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9932
_reflns_number_total             15354
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            cm8b03366_si_004.cif
_cod_data_source_block           cu_a004_0m_pl
_cod_original_sg_symbol_H-M      'R -3'
_cod_database_code               4003385
_shelx_estimated_absorpt_t_max   0.933
_shelx_estimated_absorpt_t_min   0.703
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, {H43,H43A,H43B} of C43, All C(H,H) groups
 At 1.5 times of:
  {H24A,H24B,H24C} of C24, {H23A,H23B,H23C} of C23, {H58A,H58B,H58C} of C58,
  {H13A,H13B,H13C} of C13, {H69A,H69B,H69C} of C69, {H57A,H57B,H57C} of C57,
  {H56A,H56B,H56C} of C56, {H22A,H22B,H22C} of C22, {H63C,H63D,H63E} of C63,
  {H34A,H34B,H34C} of C34, {H68A,H68B,H68C} of C68, {H21A,H21B,H21C} of C21,
  {H47A,H47B,H47C} of C47
2. Restrained distances
 C30-C32 = C31-C33
 2.543 with sigma of 0.04
 C31-C32
 1.522 with sigma of 0.02
 C29-C30 = C30-C31 = C32-C33 = C33-C34
 1.52 with sigma of 0.005
 C29-C31 = C32-C34
 2.534 with sigma of 0.01
 C68-C67 = C67-C66
 1.52 with sigma of 0.02
 C67-C63
 2.543 with sigma of 0.04
 C66-C63
 1.522 with sigma of 0.02
 C40-C48 = C40-C42
 1.52 with sigma of 0.005
 C43-C42
 1.52 with sigma of 0.005
 C44-C43
 1.52 with sigma of 0.005
 C44-C45
 1.52 with sigma of 0.005
 C12-C11 = C13-C12
 1.52 with sigma of 0.005
 C10-C9
 1.52 with sigma of 0.005
 C66-C67 = C67-C68
 1.52 with sigma of 0.005
 C46-C45
 1.52 with sigma of 0.005
 C44-C45 = C45-C46 = C44-C43
 1.52 with sigma of 0.005
 C47-C46
 1.52 with sigma of 0.005
 C68-C66 = C63-C61
 2.534 with sigma of 0.04
 C35-C61
 1.52 with sigma of 0.005
 C62-C63
 1.52 with sigma of 0.002
 C48-C43
 1.52 with sigma of 0.005
 C40-C48 \\sim C40-C42
 with sigma of 0.002
 C62-C61 \\sim C64-C65
 with sigma of 0.002
 C64-C63 \\sim C62-C63
 with sigma of 0.002
 C35-C61 \\sim C65-C35
 with sigma of 0.002
3. Uiso/Uaniso restraints and constraints
Uanis(C35) \\sim Ueq: with sigma of 0.003 and sigma for terminal atoms of 0.006
Uanis(C42) \\sim Ueq: with sigma of 0.004 and sigma for terminal atoms of 0.008
Uanis(C42) = Uanis(C48)
Uanis(C61) = Uanis(C65)
Uanis(C64) = Uanis(C62)
4. Rigid body (RIGU) restrains
 C11, C8, C9, C10, C13, C12
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 S1, S2, C3, C27, C28, C2, C1, C29, C35, C37, C36
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C29, C30, C31, C32, C33, C34
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 O3, O4, C53, N3, N4, C52, C59, C60, C51, C54, C57, C69, C55, C56, C58
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C48, C42, C43, C44, C45
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C48, C42, C43, C44, C45, C46, C47
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C35, C68, C67, C66, C63, C61, C62, C65, C64
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
5. Others
 Sof(H63C)=Sof(H63D)=Sof(H63E)=Sof(C65)=Sof(H65A)=Sof(H65B)=Sof(C64)=Sof(H64A)=
 Sof(H64B)=1-FVAR(1)
 Sof(H63A)=Sof(H63B)=Sof(C61)=Sof(H61A)=Sof(H61B)=Sof(C62)=Sof(H62A)=Sof(H62B)=
 FVAR(1)
 Sof(C48)=Sof(H48A)=Sof(H48B)=Sof(H43)=1-FVAR(2)
 Sof(C42)=Sof(H42A)=Sof(H42B)=Sof(H43A)=Sof(H43B)=FVAR(2)
6.a Secondary CH2 refined with riding coordinates:
 C11(H11A,H11B), C8(H8A,H8B), C9(H9A,H9B), C10(H10A,H10B), C48(H48A,H48B),
 C42(H42A,H42B), C12(H12A,H12B), C29(H29A,H29B), C30(H30A,H30B), C31(H31A,H31B),
  C32(H32A,H32B), C33(H33A,H33B), C67(H67A,H67B), C66(H66A,H66B), C63(H63A,
 H63B), C61(H61A,H61B), C62(H62A,H62B), C65(H65A,H65B), C64(H64A,H64B),
 C43(H43A,H43B), C44(H44A,H44B), C45(H45A,H45B), C46(H46A,H46B)
6.b Aromatic/amide H refined with riding coordinates:
 C25(H25), C16(H16), C26(H26), C15(H15), C7(H7), C59(H59), C27(H27), C60(H60),
 C51(H51), C50(H50), C36(H36), C43(H43)
6.c Idealised Me refined as rotating group:
 C21(H21A,H21B,H21C), C23(H23A,H23B,H23C), C24(H24A,H24B,H24C), C22(H22A,H22B,
 H22C), C57(H57A,H57B,H57C), C69(H69A,H69B,H69C), C56(H56A,H56B,H56C), C58(H58A,
 H58B,H58C), C13(H13A,H13B,H13C), C34(H34A,H34B,H34C), C68(H68A,H68B,H68C),
 C63(H63C,H63D,H63E), C47(H47A,H47B,H47C)
;
_shelx_res_checksum              36817
_shelx_hkl_checksum              69768
_shelx_shelxl_version_number     2014/7
_olex2_submission_special_instructions 'No special instructions were received'