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_7060076
_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         'C37 H57 I2 N2 O2 Tb'
_chemical_formula_sum            'C37 H57 I2 N2 O2 Tb'
_chemical_formula_weight         974.56
_chemical_properties_physical    Air-sensitive,Moisture-sensitive
_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             2020-07-22
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2020-07-24 deposited with the CCDC.	2020-10-20 downloaded from the CCDC.
;
_cell_angle_alpha                102.7210(10)
_cell_angle_beta                 106.1380(10)
_cell_angle_gamma                97.7610(10)
_cell_formula_units_Z            8
_cell_length_a                   19.1978(6)
_cell_length_b                   19.5799(6)
_cell_length_c                   22.8398(8)
_cell_measurement_reflns_used    9896
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      26.25
_cell_measurement_theta_min      2.27
_cell_volume                     7866.1(4)
_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                 CCD
_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 0.995
_diffrn_measurement_device       '\k-geometry diffractometer'
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\w and \f scans'
_diffrn_radiation_monochromator  graphite
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.0329
_diffrn_reflns_av_unetI/netI     0.0607
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.995
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -24
_diffrn_reflns_limit_k_max       24
_diffrn_reflns_limit_k_min       -23
_diffrn_reflns_limit_l_max       27
_diffrn_reflns_limit_l_min       -28
_diffrn_reflns_number            71164
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.995
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         26.450
_diffrn_reflns_theta_min         0.964
_diffrn_source                   'sealed tube'
_exptl_absorpt_coefficient_mu    3.399
_exptl_absorpt_correction_T_max  0.7454
_exptl_absorpt_correction_T_min  0.6620
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2012/1 (Bruker,2012) was used for absorption correction. wR2(int) was 0.0542 before and 0.0431 after correction. The Ratio of minimum to maximum transmission is 0.8881. The \l/2 correction factor is 0.0015.'
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.646
_exptl_crystal_description       block
_exptl_crystal_F_000             3840
_exptl_crystal_preparation       Luminescent
_exptl_crystal_size_max          0.35
_exptl_crystal_size_mid          0.25
_exptl_crystal_size_min          0.25
_refine_diff_density_max         1.671
_refine_diff_density_min         -1.120
_refine_diff_density_rms         0.136
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.015
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1663
_refine_ls_number_reflns         32268
_refine_ls_number_restraints     118
_refine_ls_restrained_S_all      1.021
_refine_ls_R_factor_all          0.0906
_refine_ls_R_factor_gt           0.0459
_refine_ls_shift/su_max          0.061
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0438P)^2^+13.9301P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0993
_refine_ls_wR_factor_ref         0.1202
_reflns_Friedel_coverage         0.000
_reflns_number_gt                19513
_reflns_number_total             32268
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d0nj04201c2.cif
_cod_data_source_block           moa50
_cod_depositor_comments
'Adding full bibliography for 7060074--7060081.cif.'
_cod_database_code               7060076
_shelx_shelxl_version_number     2017/1
_shelx_estimated_absorpt_t_max   0.484
_shelx_estimated_absorpt_t_min   0.382
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups, All C(H,H,H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Restrained distances
 C2-C334 \\sim C335-C334 \\sim C337-C336 \\sim C1-C337
 with sigma of 0.02
 C335-C336 \\sim C2-C1
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C433) \\sim Ueq, Uanis(C432) \\sim Ueq, Uanis(C431) \\sim Ueq,
Uanis(C430) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(C417) \\sim Ueq, Uanis(C415) \\sim Ueq, Uanis(C416) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
4. Rigid body (RIGU) restrains
 C334, C337, C1, C2
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C334, C337, C335, C336
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 O401, C430, C431, C432, C433
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
 C415, C416, C417
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
5. Others
 Sof(Tb41)=Sof(I42A)=1-FVAR(1)
 Sof(Tb1)=Sof(I42B)=FVAR(1)
 Sof(H33K)=Sof(H33L)=Sof(H33O)=Sof(H33P)=Sof(C335)=Sof(H33Q)=Sof(H33R)=
 Sof(C336)=Sof(H33S)=Sof(H33T)=1-FVAR(2)
 Sof(H33I)=Sof(H33J)=Sof(H33M)=Sof(H33N)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(C2)=
 Sof(H2A)=Sof(H2B)=FVAR(2)
6.a Ternary CH refined with riding coordinates:
 C112(H112), C115(H115), C124(H124), C127(H127), C212(H212), C215(H215),
 C224(H224), C227(H227), C312(H312), C315(H315), C324(H324), C327(H327),
 C412(H412), C415(H415), C424(H424), C427(H427)
6.b Secondary CH2 refined with riding coordinates:
 C130(H13A,H13B), C131(H13C,H13D), C132(H13E,H13F), C133(H13G,H13H), C134(H13I,
 H13J), C135(H13K,H13L), C136(H13M,H13N), C137(H13O,H13P), C230(H23A,H23B),
 C231(H23C,H23D), C232(H23E,H23F), C233(H23G,H23H), C234(H23I,H23J), C235(H23K,
 H23L), C236(H23M,H23N), C237(H23O,H23P), C330(H33A,H33B), C331(H33C,H33D),
 C332(H33E,H33F), C333(H33G,H33H), C334(H33K,H33L), C334(H33I,H33J), C337(H33O,
 H33P), C337(H33M,H33N), C1(H1A,H1B), C2(H2A,H2B), C335(H33Q,H33R), C336(H33S,
 H33T), C430(H43A,H43B), C431(H43C,H43D), C432(H43E,H43F), C433(H43G,H43H),
 C434(H43I,H43J), C435(H43K,H43L), C436(H43M,H43N), C437(H43O,H43P)
6.c Aromatic/amide H refined with riding coordinates:
 C102(H102), C108(H108), C109(H109), C110(H110), C120(H120), C121(H121),
 C122(H122), C202(H202), C208(H208), C209(H209), C210(H210), C220(H220),
 C221(H221), C222(H222), C302(H302), C308(H308), C309(H309), C310(H310),
 C320(H320), C321(H321), C322(H322), C402(H402), C408(H408), C409(H409),
 C410(H410), C420(H420), C421(H421), C422(H422)
6.d Idealised Me refined as rotating group:
 C104(H10A,H10B,H10C), C105(H10D,H10E,H10F), C113(H11A,H11B,H11C), C114(H11D,
 H11E,H11F), C116(H11G,H11H,H11I), C117(H11J,H11K,H11L), C125(H12A,H12B,H12C),
 C126(H12D,H12E,H12F), C128(H12G,H12H,H12I), C129(H12J,H12K,H12L), C204(H20A,
 H20B,H20C), C205(H20D,H20E,H20F), C213(H21A,H21B,H21C), C214(H21D,H21E,H21F),
 C216(H21G,H21H,H21I), C217(H21J,H21K,H21L), C225(H22A,H22B,H22C), C226(H22D,
 H22E,H22F), C228(H22G,H22H,H22I), C229(H22J,H22K,H22L), C304(H30A,H30B,H30C),
 C305(H30D,H30E,H30F), C313(H31A,H31B,H31C), C314(H31D,H31E,H31F), C316(H31G,
 H31H,H31I), C317(H31J,H31K,H31L), C325(H32A,H32B,H32C), C326(H32D,H32E,H32F),
 C328(H32G,H32H,H32I), C329(H32J,H32K,H32L), C404(H40A,H40B,H40C), C405(H40D,
 H40E,H40F), C413(H41A,H41B,H41C), C414(H41D,H41E,H41F), C416(H41G,H41H,H41I),
 C417(H41J,H41K,H41L), C425(H42A,H42B,H42C), C426(H42D,H42E,H42F), C428(H42G,
 H42H,H42I), C429(H42J,H42K,H42L)
;
_shelx_res_checksum              22320
_olex2_submission_special_instructions 'No special instructions were received'