Synthesis, Spectroscopic Properties, and Photoconductivity of Black Absorbers Consisting of Pt(Bipyridine)(Dithiolate) Charge Transfer Complexes in the Presence and Absence of Nitrofluorenone Acceptors.
Browning, Charles; Hudson, Joshua M.; Reinheimer, Eric W.; Kuo, Fang-Ling; McDougald, Jr, Roy N; Rabaâ, Hassan; Pan, Hongjun; Bacsa, John; Wang, Xiaoping; Dunbar, Kim R.; Shepherd, Nigel D.; Omary, Mohammad A.; Journal of the American Chemical Society  (2014) 141107065104007–; doi:10.1021/ja506583k

data_4122897
_publ_section_title
;
 Synthesis, Spectroscopic Properties, and Photoconductivity of Black
 Absorbers Consisting of Pt(Bipyridine)(Dithiolate) Charge Transfer
 Complexes in the Presence and Absence of Nitrofluorenone Acceptors.
;
_journal_name_full               'Journal of the American Chemical Society'
_journal_page_first              141107065104007
_journal_paper_doi               10.1021/ja506583k
_journal_year                    2014
_chemical_formula_moiety         '2(C25 H30 N2 Pt S2), C13 H4 N4 O9, 2(C6 H6)'
_chemical_formula_sum            'C75 H76 N8 O9 Pt2 S4'
_chemical_formula_weight         1751.85
_chemical_name_systematic
;
 ?
;
_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'
_symmetry_space_group_name_Hall  '-P 2yn'
_symmetry_space_group_name_H-M   'P 1 21/n 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2014-06-27
_audit_creation_method
;
Olex2 1.2-beta
(compiled 2014.06.27 svn.r2953 for OlexSys, GUI svn.r4855)
;
_audit_update_record
;
2014-06-27 # Formatted by publCIF

;
_cell_angle_alpha                90
_cell_angle_beta                 92.19(3)
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   11.257(2)
_cell_length_b                   26.004(5)
_cell_length_c                   24.165(5)
_cell_measurement_reflns_used    0
_cell_measurement_temperature    100
_cell_measurement_theta_max      0.000
_cell_measurement_theta_min      0.000
_cell_volume                     7069(2)
_computing_cell_refinement       'SAINT v6.28A (Bruker, 2002)'
_computing_data_collection       'FRAMBO V4.0 (Bruker AXS Inc, 2013)'
_computing_data_reduction        'SAINT v6.28A (Bruker, 2002)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL-1997 (Sheldrick, 2008)'
_computing_structure_solution    'ShelXS (Sheldrick, 2008)'
_diffrn_ambient_temperature      100
_diffrn_detector                 'MWPC area detector'
_diffrn_detector_area_resol_mean 10.24
_diffrn_measured_fraction_theta_full 0.694
_diffrn_measured_fraction_theta_max 0.872
_diffrn_measurement_device_type  'Bruker HiStar-GADDS with a D8 goniometer'
_diffrn_measurement_method       '\w scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.2507
_diffrn_reflns_av_unetI/netI     0.3484
_diffrn_reflns_Laue_measured_fraction_full 0.694
_diffrn_reflns_Laue_measured_fraction_max 0.872
_diffrn_reflns_limit_h_max       12
_diffrn_reflns_limit_h_min       -12
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -28
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -25
_diffrn_reflns_number            30849
_diffrn_reflns_point_group_measured_fraction_full 0.694
_diffrn_reflns_point_group_measured_fraction_max 0.872
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         58.969
_diffrn_reflns_theta_min         2.497
_exptl_absorpt_coefficient_mu    8.918
_exptl_absorpt_correction_T_max  0.7516
_exptl_absorpt_correction_T_min  0.5686
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2012/1 (Bruker,2012) was used for absorption correction.
wR2(int) was 0.0969 before and 0.0748 after correction.
The Ratio of minimum to maximum transmission is 0.7565.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            blue
_exptl_crystal_colour_primary    blue
_exptl_crystal_density_diffrn    1.646
_exptl_crystal_description       plate
_exptl_crystal_F_000             3496
_exptl_crystal_recrystallization_method
'The material was recrystallised from --- by slow evaporation'
_exptl_crystal_size_max          0.21
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.04
_refine_diff_density_max         1.525
_refine_diff_density_min         -1.087
_refine_diff_density_rms         0.187
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   0.919
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     902
_refine_ls_number_reflns         8873
_refine_ls_number_restraints     730
_refine_ls_restrained_S_all      0.886
_refine_ls_R_factor_all          0.2769
_refine_ls_R_factor_gt           0.0931
_refine_ls_shift/su_max          0.039
_refine_ls_shift/su_mean         0.002
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0865P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1707
_refine_ls_wR_factor_ref         0.2442
_reflns_Friedel_coverage         0.000
_reflns_number_gt                2834
_reflns_number_total             8873
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ja506583k_si_001.cif
_cod_data_source_block           compound3
_cod_database_code               4122897
_shelxl_version_number           2013-4
_shelx_estimated_absorpt_t_max   0.717
_shelx_estimated_absorpt_t_min   0.256
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 O8-N4 = O4-N2 = O5-N2 = O6-N3 = O7-N3 = N4-O9 = O2-N1 = N1-O3
 1.1968 with sigma of 0.002
 C18A-C20A
 1.544 with sigma of 0.02
 C18A-C19A
 1.544 with sigma of 0.02
 C18A-C21A
 1.544 with sigma of 0.02
 C20A-C21A
 2.49 with sigma of 0.02
 C20A-C19A
 2.49 with sigma of 0.02
 C19A-C21A
 2.49 with sigma of 0.02
 C18C-C20C
 1.544 with sigma of 0.02
 C18C-C19C
 1.544 with sigma of 0.02
 C18C-C21C
 1.544 with sigma of 0.02
 C20C-C21C
 2.49 with sigma of 0.02
 C20C-C19C
 2.49 with sigma of 0.02
 C19C-C21C
 2.49 with sigma of 0.02
 C6-N2 = C9-N3 = N4-C11 = C4-N1
 1.54966 with sigma of 0.005
 C18C-C10A \\sim C18A-C10A
 with sigma of 0.005
 C9S-C8S \\sim C8S-C7S \\sim C7S-C12S \\sim C12S-C11S \\sim C11S-C10S \\sim
C9S-C10S
 with sigma of 0.005
 C6S-C1S \\sim C2S-C1S \\sim C3S-C2S \\sim C4S-C3S \\sim C5S-C4S \\sim C6S-C5S
 with sigma of 0.005
3. Restrained planarity
 C2, C3, C4, C5, C6, C7
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
Uanis(C12A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(N2A) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C10) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C13) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(N4) \\sim Ueq, Uanis(O9) \\sim Ueq, Uanis(O8) \\sim Ueq: with sigma of
0.005 and sigma for terminal atoms of 0.01
Uanis(C4B) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C2B) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C14B) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C12B) \\sim Ueq, Uanis(C11B) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C1S) \\sim Ueq, Uanis(C2S) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C2) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(O1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C3) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C6) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.004
Uanis(C18A) = Uanis(C18C)
Uanis(C19A) = Uanis(C19C) = Uanis(C20A) = Uanis(C20C) = Uanis(C21A) =
Uanis(C21C)
5. Rigid body (RIGU) restrains
 C1A, S1A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C2A, S2A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C2A, C1A, C6A, C5A, C4A, C3A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C4A, C7A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 N1A, Pt1A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 N2A, Pt1A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 N1A, C8A, C9A, C10A, C11A, C12A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C12A, C13A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C13A, N2A, C17A, C16A, C15A, C14A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C15A, C22A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C25A, C22A, C23A, C24A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C10A, C18A, C18C
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C18A, C21A, C20A, C19A
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C4, N1, O3, O2
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C11, N4, O9, O8
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 S1B, C1B, S2B, C2B, C6B, C5B, C3B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C5B, C7B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C2B, S2B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 S1B, C1B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 N2B, C17B, C16B, C15B, C14B, C13B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C15B, C22B, C24B, C25B, C23B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C13B, C12B, C11B, C10B, C9B, C8B, N1B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C10B, C18B, C20B, C19B, C21B
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C11S, C7S, H7S, C8S, C12S, H8S, C9S, H12S, H9S, C10S, H11S, H10S
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C4S, C1S, H1S, C2S, C6S, H2S, C3S, C5S, H6S, H3S, H5S, H4S
 with sigma for 1-2 distances of 0.002 and sigma for 1-3 distances of 0.002
 C8, C13, C12, C11, C9
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C1, O1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C13, C8, C7, C2, C1
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C6, N2, O4, O5
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C7, C6, C5, C4, C3, C2
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
6. Others
 Fixed Sof: C18A(0.5) C18C(0.5) C19A(0.5) H19A(0.5) H19B(0.5) H19C(0.5)
 C19C(0.5) H19D(0.5) H19E(0.5) H19F(0.5) C20A(0.5) H20A(0.5) H20B(0.5)
 H20C(0.5) C20C(0.5) H20D(0.5) H20E(0.5) H20F(0.5) C21A(0.5) H21A(0.5)
 H21B(0.5) H21C(0.5) C21C(0.5) H21D(0.5) H21E(0.5) H21F(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C3A(H3A), C5A(H5A), C6A(H6A), C8A(H8A), C9A(H9A), C11A(H11A), C14A(H14A),
 C16A(H16A), C17A(H17A), C3B(H3B), C4B(H4B), C6B(H6B), C8B(H8B), C9B(H9B),
 C11B(H11B), C14B(H14B), C16B(H16B), C17B(H17B), C3(H3), C5(H5), C10(H10),
 C12(H12), C7S(H7S), C8S(H8S), C9S(H9S), C10S(H10S), C11S(H11S), C12S(H12S),
 C1S(H1S), C2S(H2S), C3S(H3S), C4S(H4S), C5S(H5S), C6S(H6S)
7.b Idealised Me refined as rotating group:
 C7A(H7AA,H7AB,H7AC), C19A(H19A,H19B,H19C), C19C(H19D,H19E,H19F), C20A(H20A,
 H20B,H20C), C20C(H20D,H20E,H20F), C21A(H21A,H21B,H21C), C21C(H21D,H21E,H21F),
 C23A(H23A,H23B,H23C), C24A(H24A,H24B,H24C), C25A(H25A,H25B,H25C), C7B(H7BA,
 H7BB,H7BC), C19B(H19G,H19H,H19I), C20B(H20G,H20H,H20I), C21B(H21G,H21H,H21I),
 C23B(H23D,H23E,H23F), C24B(H24D,H24E,H24F), C25B(H25D,H25E,H25F)
;
_olex2_diffrn_ambient_temperature_device 'Oxford Cryosystems'
_olex2_exptl_crystal_mounting_method
'The crystal was mounted on a loop with paratone oil'
_olex2_submission_special_instructions 'No special instructions were received'