Tipping the polaron‒bipolaron balance: concentration and spin effects in doped oligo(aniline)s observed by UV-vis-NIR and TD-DFT
Mills, Benjamin M.; Shao, Zhecheng; Flynn, Stephanie R.; Rannou, Patrice; Lindsay, David M.; Fey, Natalie; Faul, Charl F. J.; Molecular Systems Design & Engineering 4 (2019) 103–; doi:10.1039/C8ME00082D

data_1554193
_publ_section_title
;
 Tipping the polaron--bipolaron balance: concentration and spin effects in
 doped oligo(aniline)s observed by UV-vis-NIR and TD-DFT
;
_journal_issue                   1
_journal_name_full               'Molecular Systems Design &amp; Engineering'
_journal_page_first              103
_journal_paper_doi               10.1039/C8ME00082D
_journal_volume                  4
_journal_year                    2019
_chemical_formula_moiety         'C30 H26 N4, 2(Cl O4), 2(C4 H8 O)'
_chemical_formula_sum            'C38 H42 Cl2 N4 O10'
_chemical_formula_weight         785.65
_chemical_name_common
'Phenyl-capped tetra(aniline)-ES bis(perchlorate) tetrahydrofuran solvate; [TANI-ES](ClO4)2.2THF'
_chemical_name_systematic
'N1,N1?-(1,4-phenylene)-bis(N4-phenylbenzene-1,4-diamine) dication bis(perchlorate) tetrahydrofuran solvate'
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2yn'
_space_group_name_H-M_alt        'P 1 21/n 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     iterative
_audit_creation_date             2016-09-26
_audit_creation_method
;
Olex2 1.2
(compiled 2016.09.09 svn.r3337 for OlexSys, GUI svn.r5227)
;
_audit_update_record
;
2017-09-22 deposited with the CCDC.
2018-12-03 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.267(6)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   7.6185(7)
_cell_length_b                   16.5025(16)
_cell_length_c                   14.1512(14)
_cell_measurement_reflns_used    6136
_cell_measurement_temperature    100
_cell_measurement_theta_max      66.049
_cell_measurement_theta_min      4.117
_cell_volume                     1777.8(3)
_computing_cell_refinement       'SAINT v8.34A (Bruker, 2013)'
_computing_data_reduction        'SAINT v8.34A (Bruker, 2013)'
_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
;
Superflip (Palatinus & Chapuis, 2007;Palatinus & van der Lee, 2008;
Palatinus et al., 2012)
;
_diffrn_ambient_temperature      100
_diffrn_detector                 'Bruker Pt135 CCD area detector'
_diffrn_detector_type            'CCD area detector'
_diffrn_measured_fraction_theta_full 0.984
_diffrn_measured_fraction_theta_max 0.984
_diffrn_measurement_device       'Bruker Mircostar Rotating anode'
_diffrn_measurement_device_type  'Bristol Microstar'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0982
_diffrn_reflns_av_unetI/netI     0.0550
_diffrn_reflns_Laue_measured_fraction_full 0.984
_diffrn_reflns_Laue_measured_fraction_max 0.984
_diffrn_reflns_limit_h_max       7
_diffrn_reflns_limit_h_min       -9
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       16
_diffrn_reflns_limit_l_min       -15
_diffrn_reflns_number            26744
_diffrn_reflns_point_group_measured_fraction_full 0.984
_diffrn_reflns_point_group_measured_fraction_max 0.984
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         67.165
_diffrn_reflns_theta_min         4.117
_diffrn_source                   'micro-focus rotating anode'
_exptl_absorpt_coefficient_mu    2.211
_exptl_absorpt_correction_T_max  0.7529
_exptl_absorpt_correction_T_min  0.3256
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2014/4 (Bruker,2014/4) was used for absorption correction.
wR2(int) was 0.1650 before and 0.0840 after correction.
The Ratio of minimum to maximum transmission is 0.4325.
The \l/2 correction factor is 0.00150.
;
_exptl_crystal_colour            'red with metallic lustre'
_exptl_crystal_colour_lustre     metallic
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.468
_exptl_crystal_description       needle
_exptl_crystal_F_000             824
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: tetrahydrofuran'
_exptl_crystal_size_max          0.2
_exptl_crystal_size_mid          0.07
_exptl_crystal_size_min          0.04
_refine_diff_density_max         0.466
_refine_diff_density_min         -0.447
_refine_diff_density_rms         0.079
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.070
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     298
_refine_ls_number_reflns         3127
_refine_ls_number_restraints     190
_refine_ls_restrained_S_all      1.067
_refine_ls_R_factor_all          0.0752
_refine_ls_R_factor_gt           0.0582
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0734P)^2^+1.9502P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1386
_refine_ls_wR_factor_ref         0.1506
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2551
_reflns_number_total             3127
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8me00082d2.cif
_cod_data_source_block           phphtaniesperc1_0m
_cod_database_code               1554193
_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
2. Restrained distances
 Cl1-O1 \\sim Cl1-O2 \\sim Cl1-O3 \\sim Cl1-O4 \\sim Cl1A-O1A \\sim Cl1A-O2A
\\sim Cl1A-O3A \\sim Cl1A-O4A
 with sigma of 0.01
 O1-O2 \\sim O1-O3 \\sim O1-O4 \\sim O1A-O2A \\sim O1A-O3A \\sim O1A-O4A
 with sigma of 0.01
 O2-O3 \\sim O3-O4 \\sim O4-O2 \\sim O2A-O3A \\sim O3A-O4A \\sim O4A-O2A
 with sigma of 0.01
3. Uiso/Uaniso restraints and constraints
Cl1 \\sim O1 \\sim O2 \\sim O3 \\sim O4 \\sim Cl1A \\sim O1A \\sim O2A \\sim
O3A \\sim O4A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
4. Others
 Sof(Cl1A)=Sof(O1A)=Sof(O2A)=Sof(O3A)=Sof(O4A)=1-FVAR(1)
 Sof(Cl1)=Sof(O1)=Sof(O2)=Sof(O3)=Sof(O4)=FVAR(1)
5.a Secondary CH2 refined with riding coordinates:
 C16(H16A,H16B), C17(H17A,H17B), C18(H18A,H18B), C19(H19A,H19B)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C3(H3), C4(H4), C5(H5), C6(H6), C8(H8), C9(H9), C11(H11), C12(H12),
 C14(H14), C15(H15)
;
_shelx_res_checksum              24763
_shelx_hkl_checksum              30095
_olex2_submission_special_instructions 'No special instructions were received'