Synthesis and Optical Properties of Donor-Acceptor-Type 1,3,5,9-Tetraarylpyrenes: Controlling Intramolecular Charge-Transfer Pathways by the Change of π-Conjugation Directions for Emission Color Modulations.
Liu, Rui; Ran, Huijuan; Zhao, Zhen; Yang, Xueli; Zhang, Jiali; Chen, Lijuan; Sun, Huaming; Hu, Jian-Yong; ACS omega 3 (2018) 5866–5875; doi:10.1021/acsomega.8b00583

data_4515961
_publ_section_title
;
 Synthesis and Optical Properties of Donor-Acceptor-Type
 1,3,5,9-Tetraarylpyrenes: Controlling Intramolecular Charge-Transfer
 Pathways by the Change of \p-Conjugation Directions for Emission Color
 Modulations.
;
_journal_issue                   5
_journal_name_full               'ACS omega'
_journal_page_first              5866
_journal_page_last               5875
_journal_paper_doi               10.1021/acsomega.8b00583
_journal_volume                  3
_journal_year                    2018
_chemical_formula_moiety         'C46 H38 O2'
_chemical_formula_sum            'C46 H38 O2'
_chemical_formula_weight         622.76
_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             2018-04-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.04.26 svn.r3504 for OlexSys, GUI svn.r5492)
;
_cell_angle_alpha                99.883(6)
_cell_angle_beta                 90.591(6)
_cell_angle_gamma                94.939(6)
_cell_formula_units_Z            8
_cell_length_a                   11.561(2)
_cell_length_b                   20.663(4)
_cell_length_c                   28.603(5)
_cell_measurement_reflns_used    9903
_cell_measurement_temperature    153
_cell_measurement_theta_max      68.194
_cell_measurement_theta_min      2.898
_cell_volume                     6704(2)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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    'XT (Sheldrick, 2015)'
_diffrn_ambient_temperature      153.03
_diffrn_measured_fraction_theta_full 0.991
_diffrn_measured_fraction_theta_max 0.985
_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  0.0625
_diffrn_reflns_av_unetI/netI     0.0359
_diffrn_reflns_Laue_measured_fraction_full 0.991
_diffrn_reflns_Laue_measured_fraction_max 0.985
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -24
_diffrn_reflns_limit_l_max       34
_diffrn_reflns_limit_l_min       -34
_diffrn_reflns_number            179936
_diffrn_reflns_point_group_measured_fraction_full 0.991
_diffrn_reflns_point_group_measured_fraction_max 0.985
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         68.459
_diffrn_reflns_theta_min         2.179
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.569
_exptl_absorpt_correction_T_max  0.7130
_exptl_absorpt_correction_T_min  0.6291
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1455 before and 0.1085 after correction. The Ratio of minimum to maximum transmission is 0.8823. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            'dull light colourless'
_exptl_crystal_colour_lustre     dull
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.234
_exptl_crystal_description       block
_exptl_crystal_F_000             2640
_exptl_crystal_size_max          0.5
_exptl_crystal_size_mid          0.4
_exptl_crystal_size_min          0.3
_refine_diff_density_max         0.646
_refine_diff_density_min         -0.402
_refine_diff_density_rms         0.047
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.046
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1854
_refine_ls_number_reflns         24274
_refine_ls_number_restraints     631
_refine_ls_restrained_S_all      1.048
_refine_ls_R_factor_all          0.0670
_refine_ls_R_factor_gt           0.0638
_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^)+(0.1118P)^2^+2.5018P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1875
_refine_ls_wR_factor_ref         0.1912
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22207
_reflns_number_total             24274
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            ao8b00583_si_002.cif
_cod_data_source_block           s
_cod_database_code               4515961
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.848
_shelx_estimated_absorpt_t_min   0.764
_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
 C157-C155 = C155-C1B = C158-C155 = C155-C1C = C156-C155 = C155-C1A
 1.5 with sigma of 0.01
 C1B-C1C
 2.5 with sigma of 0.02
 C157-C158
 2.5 with sigma of 0.02
 C157-C156
 2.5 with sigma of 0.02
 C156-C158
 2.5 with sigma of 0.02
3. Rigid bond restraints
 C21A, C26A, C25A, C24A, C23A, C22A, O1A, C45A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O1, C21, C24, C22, C23, C25, C26, C45
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
4. Uiso/Uaniso restraints and constraints
C21A \\sim C26A \\sim C25A \\sim C24A \\sim C23A \\sim C22A \\sim O1A \\sim
C45A: within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
O1 \\sim C21 \\sim C24 \\sim C22 \\sim C23 \\sim C25 \\sim C26 \\sim C45:
within 1.7A with sigma of 0.04 and sigma for terminal atoms of 0.08
C158 \\sim C155 \\sim C156 \\sim C157 \\sim C1A \\sim C1B \\sim C1C: within 2A
with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C45A) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(C42) \\sim Ueq, Uanis(C46)
\\sim Ueq, Uanis(C43) \\sim Ueq, Uanis(C41) \\sim Ueq, Uanis(C44) \\sim Ueq,
Uanis(C40) \\sim Ueq, Uanis(C39) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C15)
\\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C14) \\sim Ueq, Uanis(C2) \\sim Ueq,
Uanis(C4) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C7) \\sim
Ueq, Uanis(C5) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C33) \\sim Ueq,
Uanis(C12) \\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C17)
\\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C11) \\sim Ueq, Uanis(C38) \\sim Ueq,
Uanis(C34) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C21A) \\sim Ueq, Uanis(C18)
\\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C19) \\sim Ueq, Uanis(C27) \\sim Ueq,
Uanis(C37) \\sim Ueq, Uanis(C35) \\sim Ueq, Uanis(C22) \\sim Ueq, Uanis(C26)
\\sim Ueq, Uanis(C26A) \\sim Ueq, Uanis(C22A) \\sim Ueq, Uanis(C32) \\sim Ueq,
Uanis(C28) \\sim Ueq, Uanis(C36) \\sim Ueq, Uanis(C23) \\sim Ueq, Uanis(C25)
\\sim Ueq, Uanis(C25A) \\sim Ueq, Uanis(C23A) \\sim Ueq, Uanis(C31) \\sim Ueq,
Uanis(C29) \\sim Ueq, Uanis(C24) \\sim Ueq, Uanis(C24A) \\sim Ueq, Uanis(C30)
\\sim Ueq, Uanis(O1) \\sim Ueq, Uanis(O1A) \\sim Ueq, Uanis(C45) \\sim Ueq:
with sigma of 0.1 and sigma for terminal atoms of 0.2
Uanis(C158) \\sim Ueq, Uanis(C155) \\sim Ueq, Uanis(C156) \\sim Ueq,
Uanis(C157) \\sim Ueq, Uanis(C1A) \\sim Ueq, Uanis(C1B) \\sim Ueq, Uanis(C1C)
\\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C45A) \\sim Ueq, Uanis(O1A) \\sim Ueq, Uanis(C24A) \\sim Ueq, Uanis(C25A)
\\sim Ueq, Uanis(C23A) \\sim Ueq, Uanis(C22A) \\sim Ueq, Uanis(C26A) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C45A) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(O1A) \\sim Ueq, Uanis(C45A) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
5. Rigid body (RIGU) restrains
 C158, C155, C156, C157, C1A, C1B, C1C
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
6. Same fragment restrains
{O1A, C21A, C24A, C22A, C23A, C25A, C26A, C45A} sigma for 1-2: 0.02, 1-3: 0.04
as
{O1, C21, C24, C22, C23, C25, C26, C45}
7. Others
 Sof(O1A)=Sof(C21A)=Sof(C24A)=Sof(C22A)=Sof(H22A)=Sof(C23A)=Sof(H23A)=
 Sof(C25A)=Sof(H25A)=Sof(C26A)=Sof(H26A)=Sof(C45A)=Sof(H45D)=Sof(H45E)=
 Sof(H45F)=1-FVAR(1)
 Sof(O1)=Sof(C21)=Sof(C24)=Sof(C22)=Sof(H22)=Sof(C23)=Sof(H23)=Sof(C25)=
 Sof(H25)=Sof(C26)=Sof(H26)=Sof(C45)=Sof(H45A)=Sof(H45B)=Sof(H45C)=FVAR(1)
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=Sof(C1B)=Sof(H1BA)=Sof(H1BB)=Sof(H1BC)=
 Sof(C1C)=Sof(H1CA)=Sof(H1CB)=Sof(H1CC)=1-FVAR(2)
 Sof(C158)=Sof(H15A)=Sof(H15B)=Sof(H15C)=Sof(C156)=Sof(H15D)=Sof(H15E)=
 Sof(H15F)=Sof(C157)=Sof(H15G)=Sof(H15H)=Sof(H15I)=FVAR(2)
8.a Aromatic/amide H refined with riding coordinates:
 C22(H22), C23(H23), C25(H25), C26(H26), C55(H55), C15(H15), C50(H50),
 C61(H61), C9(H9), C58(H58), C4(H4), C52(H52), C132(H132), C104(H104), C40(H40),
  C12(H12), C80(H80), C44(H44), C6(H6), C136(H136), C178(H178), C107(H107),
 C182(H182), C32(H32), C71(H71), C72(H72), C150(H150), C68(H68), C28(H28),
 C69(H69), C96(H96), C135(H135), C181(H181), C101(H101), C133(H133), C147(H147),
  C78(H78), C142(H142), C84(H84), C43(H43), C41(H41), C179(H179), C153(H153),
 C38(H38), C74(H74), C98(H98), C120(H120), C126(H126), C166(H166), C117(H117),
 C118(H118), C86(H86), C130(H130), C127(H127), C164(H164), C163(H163), C37(H37),
  C34(H34), C89(H89), C114(H114), C115(H115), C121(H121), C124(H124),
 C144(H144), C90(H90), C36(H36), C170(H170), C76(H76), C161(H161), C29(H29),
 C122(H122), C128(H128), C160(H160), C77(H77), C129(H129), C167(H167), C81(H81),
  C31(H31), C75(H75), C123(H123), C176(H176), C83(H83), C87(H87), C168(H168),
 C169(H169), C82(H82), C172(H172), C30(H30), C175(H175), C35(H35), C174(H174),
 C173(H173), C22A(H22A), C23A(H23A), C25A(H25A), C26A(H26A)
8.b Idealised Me refined as rotating group:
 C45(H45A,H45B,H45C), C184(H18D,H18E,H18F), C65(H65A,H65B,H65C), C18(H18A,H18B,
 H18C), C46(H46A,H46B,H46C), C138(H13A,H13B,H13C), C91(H91A,H91B,H91C),
 C66(H66A,H66B,H66C), C183(H18G,H18H,H18I), C137(H13D,H13E,H13F), C158(H15A,
 H15B,H15C), C20(H20A,H20B,H20C), C64(H64A,H64B,H64C), C19(H19A,H19B,H19C),
 C111(H11A,H11B,H11C), C112(H11D,H11E,H11F), C92(H92A,H92B,H92C), C156(H15D,
 H15E,H15F), C157(H15G,H15H,H15I), C110(H11G,H11H,H11I), C45A(H45D,H45E,H45F),
 C1A(H1AA,H1AB,H1AC), C1B(H1BA,H1BB,H1BC), C1C(H1CA,H1CB,H1CC)
;
_shelx_res_checksum              34386
_shelx_hkl_checksum              81914
_olex2_submission_special_instructions 'No special instructions were received'