Substituents Make a Difference: 6,6’’-modified Terpyridine Complexes with Helix Configuration and Enhanced Emission
Fu, Fan; Liu, Die; Zhao, Lili; Li, Huili; Bai, Xinyu; Chen, Mingzhao; Jiang, Zhilong; Su, Peiyang; Zhong, Wanying; Li, Yiming; Liao, Wei-Ming; He, Jun; Wang, Pingshan; Dalton Transactions  (2023) –; doi:10.1039/D2DT04006A

data_7712223
_publ_section_title
;
 Substituents Make a Difference: 6,6&#x2019;&#x2019;-modified Terpyridine
 Complexes with Helix Configuration and Enhanced Emission
;
_journal_name_full               'Dalton Transactions'
_journal_paper_doi               10.1039/D2DT04006A
_journal_year                    2023
_chemical_formula_moiety         'C70 H54 Mn N6 O4, 2(C2 F6 N O4 S2)'
_chemical_formula_sum            'C74 H54 F12 Mn N8 O12 S4'
_chemical_formula_weight         1658.43
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2022-05-01
_audit_creation_method
;
Olex2 1.5-alpha
(compiled 2021.11.18 svn.ra9532c28 for OlexSys, GUI svn.r6427)
;
_audit_update_record
;
2022-11-16 deposited with the CCDC.	2023-01-30 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 93.595(3)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   16.4958(5)
_cell_length_b                   20.9832(7)
_cell_length_c                   41.0349(14)
_cell_measurement_reflns_used    13731
_cell_measurement_temperature    119.99(15)
_cell_measurement_theta_max      29.6500
_cell_measurement_theta_min      3.1260
_cell_volume                     14175.7(8)
_computing_molecular_graphics    'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5-alpha (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      119.99(15)
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.846
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0556
_diffrn_reflns_av_unetI/netI     0.0934
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.846
_diffrn_reflns_limit_h_max       21
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       28
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       55
_diffrn_reflns_limit_l_min       -53
_diffrn_reflns_number            81943
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.846
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         29.631
_diffrn_reflns_theta_min         2.408
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    0.406
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.84891
_exptl_absorpt_correction_type   multi-scan
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.554
_exptl_crystal_description       block
_exptl_crystal_F_000             6776
_exptl_crystal_size_max          0.14
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.11
_refine_diff_density_max         1.068
_refine_diff_density_min         -0.835
_refine_diff_density_rms         0.094
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.047
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2102
_refine_ls_number_reflns         33790
_refine_ls_number_restraints     456
_refine_ls_restrained_S_all      1.060
_refine_ls_R_factor_all          0.1236
_refine_ls_R_factor_gt           0.0655
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0638P)^2^+14.3991P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1451
_refine_ls_wR_factor_ref         0.1820
_reflns_Friedel_coverage         0.000
_reflns_number_gt                20011
_reflns_number_total             33790
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d2dt04006a2.cif
_cod_data_source_block           ld232-mn-1
_cod_database_code               7712223
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.957
_shelx_estimated_absorpt_t_min   0.945
_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
 S4-N15 = N15-S3A
 1.56 with sigma of 0.02
 S4-N15 = N15-S3
 1.56 with sigma of 0.02
 S4-S3
 2.761 with sigma of 0.04
 S4-S3A
 2.761 with sigma of 0.04
 F9-F7 \\sim F9-F8 \\sim F8-F7
 with sigma of 0.02
 F9-C066 \\sim F7-C066 \\sim F8-C066
 with sigma of 0.02
 F2-C063 \\sim F2A-C063
 with sigma of 0.02
 F3A-C063 \\sim F3-C063
 with sigma of 0.02
 F1A-C063 \\sim F1-C063
 with sigma of 0.02
 F2-F1 \\sim F3-F1 \\sim F3-F2
 with sigma of 0.02
 F2A-F1A \\sim F3A-F1A \\sim F3A-F2A
 with sigma of 0.02
 S3A-O15A \\sim S3A-O16A
 with sigma of 0.02
 F9A-F7A \\sim F9A-F8A \\sim F8A-F7A
 with sigma of 0.02
 S3-N15 \\sim S3A-N15
 with sigma of 0.02
 S3-O15 \\sim S3-O16
 with sigma of 0.02
 S3A-C0 \\sim S3-C066
 with sigma of 0.02
 F9-C066 \\sim F8-C066 \\sim F7-C066
 with sigma of 0.02
 F9A-C0 \\sim F7A-C0 \\sim F8A-C0
 with sigma of 0.02
 F8-F7 \\sim F9-F7 \\sim F9-F8
 with sigma of 0.02
3. Rigid bond restraints
 S6, C05W
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.02
4. Uiso/Uaniso restraints and constraints
S3 \\sim F7 \\sim F8 \\sim F9 \\sim O15 \\sim O16 \\sim C066: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
F1 \\sim F1A \\sim F2 \\sim F2A \\sim F3 \\sim F3A \\sim C063: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
S3 \\sim S3A \\sim F7 \\sim F7A \\sim F8 \\sim F8A \\sim F9 \\sim F9A \\sim O15
\\sim O15A \\sim O16 \\sim O16A \\sim C0 \\sim C066: within 2A with sigma of
0.01 and sigma for terminal atoms of 0.02 within 2A
Uanis(F8) \\sim Ueq, Uanis(F9) \\sim Ueq, Uanis(F9A) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
5. Rigid body (RIGU) restrains
 S3
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 S3, F7, F8, F9, O15, O16, C066
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F1, F2, F3, C063
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 F1A, F2A, F3A, C063
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 S3, F7, F8, F9, O15, O16, N15, C066
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
 S3A, F7A, F8A, F9A, O15A, O16A, N15, C0
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.002
6. Others
 Sof(F1A)=Sof(F2A)=Sof(F3A)=1-FVAR(1)
 Sof(F1)=Sof(F2)=Sof(F3)=FVAR(1)
 Sof(S3A)=Sof(F7A)=Sof(F8A)=Sof(F9A)=Sof(O15A)=Sof(O16A)=Sof(C0)=1-FVAR(2)
 Sof(S3)=Sof(F7)=Sof(F8)=Sof(F9)=Sof(O15)=Sof(O16)=Sof(C066)=FVAR(2)
7.a Aromatic/amide H refined with riding coordinates:
 C36(H36), C36A(H36A), C37(H37), C37A(H37A), C38(H38), C40(H40), C40A(H40A),
 C41(H41), C41A(H41A), C43(H43), C43A(H43A), C46(H46), C46A(H46A), C48(H48),
 C48A(H48A), C49(H49), C49A(H49A), C50(H50), C50A(H50A), C53(H53), C53A(H53A),
 C54(H54), C54A(H54A), C56(H56), C56A(H56A), C57(H57), C57A(H57A), C60(H60),
 C60A(H60A), C61(H61), C61A(H61A), C62(H62), C62A(H62A), C65(H65), C65A(H65A),
 C66(H66), C66A(H66A), C68(H68), C68A(H68A), C69(H69), C69A(H69A), C1(H1),
 C1A(H1A), C2(H2), C2A(H2A), C3(H3), C3A(H3A), C5(H5), C5A(H5A), C6(H6),
 C6A(H6A), C8(H8), C8A(H8A), C11(H11), C11A(H11A), C13(H13), C13A(H13A),
 C14(H14), C14A(H14A), C15(H15), C15A(H15A), C18(H18), C18A(H18A), C19(H19),
 C19A(H19A), C21(H21), C21A(H21A), C22(H22), C22A(H22A), C25(H25), C25A(H25A),
 C26(H26), C26A(H26A), C27(H27), C27A(H27A), C30(H30), C30A(H30A), C31(H31),
 C31A(H31A), C33(H33), C33A(H33A), C34(H34), C34A(H34A)
7.b Idealised Me refined as rotating group:
 C58(H58A,H58B,H58C), C58A(H58D,H58E,H58F), C70(H70A,H70B,H70C), C70A(H70D,
 H70E,H70F), C23(H23A,H23B,H23C), C23A(H23D,H23E,H23F), C35(H35A,H35B,H35C),
 C35A(H35D,H35E,H35F)
;
_shelx_res_checksum              36158
_olex2_submission_special_instructions 'No special instructions were received'