Synthesis and luminescence studies of lanthanide complexes (Gd, Tb, Dy) with phenyl- and 2-pyridylthiolates supported by a bulky β-diketiminate ligand. Impact of the ligand environment on terbium(iii) emission
Mironova, Olga A.; Ryadun, Aleksey A.; Sukhikh, Taisiya S.; Konchenko, Sergey N.; Pushkarevsky, Nikolay A.; New Journal of Chemistry 44 (2020) 19769–19779; doi:10.1039/D0NJ04201C

data_7060081
_publ_section_title
;
 Synthesis and luminescence studies of lanthanide complexes (Gd, Tb, Dy)
 with phenyl- and 2-pyridylthiolates supported by a bulky \b-diketiminate
 ligand. Impact of the ligand environment on terbium(iii) emission
;
_journal_issue                   45
_journal_name_full               'New Journal of Chemistry'
_journal_page_first              19769
_journal_page_last               19779
_journal_paper_doi               10.1039/D0NJ04201C
_journal_volume                  44
_journal_year                    2020
_chemical_formula_moiety         '2(C41 H51 N2 S2 Tb), 2(C7 H8)'
_chemical_formula_sum            'C96 H118 N4 S4 Tb2'
_chemical_formula_weight         1774.02
_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             2020-10-01
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-10-01 deposited with the CCDC.	2020-10-20 downloaded from the CCDC.
;
_cell_angle_alpha                92.345(2)
_cell_angle_beta                 111.744(2)
_cell_angle_gamma                111.629(2)
_cell_formula_units_Z            1
_cell_length_a                   11.4580(6)
_cell_length_b                   14.6416(7)
_cell_length_c                   15.2678(6)
_cell_measurement_reflns_used    9796
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      27.92
_cell_measurement_theta_min      2.33
_cell_volume                     2164.40(18)
_computing_cell_refinement       'Bruker SAINT'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'Bruker SAINT'
_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    'ShelXT (Sheldrick, 2015)'
_diffrn_ambient_temperature      150(2)
_diffrn_detector_area_resol_mean 8.33
_diffrn_detector_type            'Bruker APEXII CCD area detector'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0315
_diffrn_reflns_av_unetI/netI     0.0306
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       15
_diffrn_reflns_limit_h_min       -15
_diffrn_reflns_limit_k_max       19
_diffrn_reflns_limit_k_min       -19
_diffrn_reflns_limit_l_max       13
_diffrn_reflns_limit_l_min       -20
_diffrn_reflns_number            36467
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.915
_diffrn_reflns_theta_min         2.002
_exptl_absorpt_coefficient_mu    1.764
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6086
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.0665 before and 0.0431 after correction. The Ratio of minimum to maximum transmission is 0.8163. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.361
_exptl_crystal_description       prism
_exptl_crystal_F_000             916
_exptl_crystal_preparation       Luminescent,Luminescent
_exptl_crystal_size_max          0.4
_exptl_crystal_size_mid          0.28
_exptl_crystal_size_min          0.25
_refine_diff_density_max         0.631
_refine_diff_density_min         -0.357
_refine_diff_density_rms         0.064
_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     675
_refine_ls_number_reflns         10281
_refine_ls_number_restraints     384
_refine_ls_restrained_S_all      1.051
_refine_ls_R_factor_all          0.0220
_refine_ls_R_factor_gt           0.0193
_refine_ls_shift/su_max          0.005
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0159P)^2^+0.8407P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0449
_refine_ls_wR_factor_ref         0.0460
_reflns_Friedel_coverage         0.000
_reflns_number_gt                9622
_reflns_number_total             10281
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0nj04201c2.cif
_cod_data_source_block           moa78
_cod_depositor_comments
'Adding full bibliography for 7060074--7060081.cif.'
_cod_database_code               7060081
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.667
_shelx_estimated_absorpt_t_min   0.539
_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
 C37-C39 \\sim C37A-C39A
 with sigma of 0.04
 C38-C40 \\sim C38A-C40A
 with sigma of 0.04
 C37-C38 \\sim C37A-C38A
 with sigma of 0.02
 C38-C39 \\sim C38A-C39A
 with sigma of 0.02
 C39-C40 \\sim C39A-C40A
 with sigma of 0.02
 S2-C37 \\sim S2A-C37A
 with sigma of 0.04
 C37-C41 \\sim C37A-C41A
 with sigma of 0.04
 C39-C41 \\sim C39A-C41A
 with sigma of 0.04
 C40-C41 \\sim C40A-C41A
 with sigma of 0.02
 S2-C41 \\sim S2A-C41A
 with sigma of 0.04
 C6U-C7U \\sim C7U-C2U \\sim C6T-C7T \\sim C7T-C2T \\sim C2V-C7V \\sim C7V-C6V
 with sigma of 0.02
 C2T-C1T \\sim C3T-C2T \\sim C4T-C3T \\sim C5T-C4T \\sim C6T-C5T \\sim C6T-C1T
\\sim C2U-C1U \\sim C3U-C2U
 \\sim C4U-C3U \\sim C5U-C4U \\sim C6U-C5U \\sim C6U-C1U \\sim C2V-C1V \\sim
C3V-C2V \\sim C4V-C3V \\sim C5V-
 C4V \\sim C6V-C5V \\sim C6V-C1V
 with sigma of 0.02
 Tb1-S2 \\sim Tb1-S2A
 with sigma of 0.02
 C7T-C1T \\sim C7U-C1U \\sim C7V-C1V
 with sigma of 0.02
3. Rigid body (RIGU) restrains
 S2A, C41A, C37A, C38A, C39A, C40A
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C3T, C1T, C2T, C6T, C7T, C5T, C4T
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C3V, C1V, C2V, C6V, C7V, C5V, C4V
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 C3U, C1U, C2U, C6U, C7U, C5U, C4U
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
 S2, C36, C37, C38, C39, C40, C41
 with sigma for 1-2 distances of 0.001 and sigma for 1-3 distances of 0.001
4. Others
 1*[Sof(C1T)+Sof(C2T)+Sof(H2T)+Sof(C3T)+Sof(H3T)+Sof(C4T)+Sof(H4T)+Sof(C5T)+
 Sof(H5T)+Sof(C6T)+Sof(H6T)+Sof(C7T)+Sof(H7TA)+Sof(H7TB)+Sof(H7TC)]+1*[Sof(C1U)+
 Sof(C2U)+Sof(H2U)+Sof(C3U)+Sof(H3U)+Sof(C4U)+Sof(H4U)+Sof(C5U)+Sof(H5U)+
 Sof(C6U)+Sof(H6U)+Sof(C7U)+Sof(H7UA)+Sof(H7UB)+Sof(H7UC)]+1*[Sof(C1V)+Sof(C2V)+
 Sof(H2V)+Sof(C3V)+Sof(H3V)+Sof(C4V)+Sof(H4V)+Sof(C5V)+Sof(H5V)+Sof(C6V)+
 Sof(H6V)+Sof(C7V)+Sof(H7VA)+Sof(H7VB)+Sof(H7VC)]=1 with esd of 0.0001
 Sof(S2A)=Sof(C37A)=Sof(H37A)=Sof(C38A)=Sof(H38A)=Sof(C39A)=Sof(H39A)=
 Sof(C40A)=Sof(H40A)=Sof(C41A)=Sof(H41A)=1-FVAR(1)
 Sof(S2)=Sof(C37)=Sof(H37)=Sof(C38)=Sof(H38)=Sof(C39)=Sof(H39)=Sof(C40)=
 Sof(H40)=Sof(C41)=Sof(H41)=FVAR(1)
 Sof(C1T)=Sof(C2T)=Sof(H2T)=Sof(C3T)=Sof(H3T)=Sof(C4T)=Sof(H4T)=Sof(C5T)=
 Sof(H5T)=Sof(C6T)=Sof(H6T)=Sof(C7T)=Sof(H7TA)=Sof(H7TB)=Sof(H7TC)=FVAR(2)
 Sof(C1U)=Sof(C2U)=Sof(H2U)=Sof(C3U)=Sof(H3U)=Sof(C4U)=Sof(H4U)=Sof(C5U)=
 Sof(H5U)=Sof(C6U)=Sof(H6U)=Sof(C7U)=Sof(H7UA)=Sof(H7UB)=Sof(H7UC)=FVAR(3)
 Sof(C1V)=Sof(C2V)=Sof(H2V)=Sof(C3V)=Sof(H3V)=Sof(C4V)=Sof(H4V)=Sof(C5V)=
 Sof(H5V)=Sof(C6V)=Sof(H6V)=Sof(C7V)=Sof(H7VA)=Sof(H7VB)=Sof(H7VC)=FVAR(4)
5.a Ternary CH refined with riding coordinates:
 C12(H12), C15(H15), C24(H24), C27(H27)
5.b Aromatic/amide H refined with riding coordinates:
 C2(H2), C8(H8), C9(H9), C10(H10), C20(H20), C21(H21), C22(H22), C31(H31),
 C32(H32), C33(H33), C34(H34), C35(H35), C37(H37), C38(H38), C39(H39), C40(H40),
  C41(H41), C2T(H2T), C3T(H3T), C4T(H4T), C5T(H5T), C6T(H6T), C37A(H37A),
 C38A(H38A), C39A(H39A), C40A(H40A), C41A(H41A), C2U(H2U), C3U(H3U), C4U(H4U),
 C5U(H5U), C6U(H6U), C2V(H2V), C3V(H3V), C4V(H4V), C5V(H5V), C6V(H6V)
5.c Idealised Me refined as rotating group:
 C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C),
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C25(H25A,H25B,H25C), C26(H26A,H26B,
 H26C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C7T(H7TA,H7TB,H7TC), C7U(H7UA,
 H7UB,H7UC), C7V(H7VA,H7VB,H7VC)
;
_shelx_res_checksum              33331
_olex2_submission_special_instructions 'No special instructions were received'