Elucidating white light emissions in Tm<sup>3+</sup>/Dy<sup>3+</sup> codoped polyoxometalates: a color tuning and energy transfer mechanism study.
Wu, Hechen; Zhi, Minna; Singh, Vikram; Li, Huafeng; Ma, Pengtao; Niu, Jingyang; Wang, Jingping; Dalton transactions (Cambridge, England : 2003) 47 (2018) 13949–13956; doi:10.1039/c8dt02671h

data_7047409
_publ_section_title
;
 Elucidating white light emissions in Tm<sup>3+</sup>/Dy<sup>3+</sup>
 codoped polyoxometalates: a color tuning and energy transfer mechanism
 study.
;
_journal_issue                   39
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              13949
_journal_page_last               13956
_journal_paper_doi               10.1039/c8dt02671h
_journal_volume                  47
_journal_year                    2018
_chemical_formula_moiety
'C8 H4 O90 P2 Tm2 W22, 6(C4 H12 N), 3[K], 66[H2O]'
_chemical_formula_sum            'C32 H208 K3 N6 O156 P2 Tm2 W22'
_chemical_formula_weight         7735.54
_space_group_crystal_system      orthorhombic
_space_group_IT_number           33
_space_group_name_Hall           'P 2c -2n'
_space_group_name_H-M_alt        'P n a 21'
_symmetry_space_group_name_Hall  'P 2c -2n'
_symmetry_space_group_name_H-M   'P n a 21'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     direct
_audit_creation_date             2018-08-08
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2018-08-24 deposited with the CCDC.
2018-08-29 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   22.095(2)
_cell_length_b                   13.0551(13)
_cell_length_c                   52.019(5)
_cell_measurement_reflns_used    9902
_cell_measurement_temperature    296(2)
_cell_measurement_theta_max      28.03
_cell_measurement_theta_min      2.19
_cell_volume                     15005(2)
_computing_cell_refinement       'SAINT v8.37A (Bruker, 2015)'
_computing_data_collection       'Bruker APEX2'
_computing_data_reduction        'SAINT v8.37A (Bruker, 2015)'
_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    'ShelXS-1997 (Sheldrick, 2008)'
_diffrn_ambient_temperature      296.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.998
_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  0.0963
_diffrn_reflns_av_unetI/netI     0.1003
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.998
_diffrn_reflns_limit_h_max       26
_diffrn_reflns_limit_h_min       -26
_diffrn_reflns_limit_k_max       15
_diffrn_reflns_limit_k_min       -13
_diffrn_reflns_limit_l_max       62
_diffrn_reflns_limit_l_min       -45
_diffrn_reflns_number            73435
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.998
_diffrn_reflns_theta_full        25.097
_diffrn_reflns_theta_max         25.097
_diffrn_reflns_theta_min         1.608
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    18.055
_exptl_absorpt_correction_T_max  0.7457
_exptl_absorpt_correction_T_min  0.1929
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
'SADABS-2016/2 (Bruker,2016/2) was used for absorption correction. wR2(int) was 0.1676 before and 0.0798 after correction. The Ratio of minimum to maximum transmission is 0.2587. The \l/2 correction factor is Not present.'
_exptl_crystal_colour            colourless
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    2.846
_exptl_crystal_description       block
_exptl_crystal_F_000             11304
_exptl_crystal_size_max          0.34
_exptl_crystal_size_mid          0.27
_exptl_crystal_size_min          0.12
_refine_diff_density_max         3.343
_refine_diff_density_min         -3.165
_refine_diff_density_rms         0.363
_refine_ls_abs_structure_details
;
 Refined as an inversion twin.
;
_refine_ls_abs_structure_Flack   0.40(2)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.054
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1364
_refine_ls_number_reflns         21850
_refine_ls_number_restraints     745
_refine_ls_restrained_S_all      1.043
_refine_ls_R_factor_all          0.0917
_refine_ls_R_factor_gt           0.0623
_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^)+(0.0450P)^2^+429.5351P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1454
_refine_ls_wR_factor_ref         0.1641
_reflns_Friedel_coverage         0.977
_reflns_Friedel_fraction_full    0.999
_reflns_Friedel_fraction_max     0.999
_reflns_number_gt                15918
_reflns_number_total             21850
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c8dt02671h2.cif
_cod_data_source_block           Tm-POM
_cod_depositor_comments          'Adding full bibliography for 7047409.cif.'
_cod_original_cell_volume        15005(3)
_cod_database_code               7047409
_shelx_shelxl_version_number     2018/1
_shelx_estimated_absorpt_t_max   0.221
_shelx_estimated_absorpt_t_min   0.064
_olex2_refinement_description
;
1. Twinned data refinement
 Scales: 0.60(2)
 0.40(2)
2. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
 At 1.5 times of:
  All C(H,H,H) groups
3. Restrained distances
 N2-C14 = N2-C15 = N3-C17 = N3-C20
 1.47 with sigma of 0.01
 N1-C9 = N1-C10 = N1-C11 = N1-C12
 1.47 with sigma of 0.01
 N2-C13 = N2-C14 = N2-C15 = N2-C16
 1.47 with sigma of 0.01
 N3-C17 = N3-C18 = N3-C19 = N3-C20
 1.47 with sigma of 0.01
 N4-C21 = N4-C22 = N4-C23 = N4-C24
 1.47 with sigma of 0.01
 N5-C25 = N5-C26 = N5-C27 = N5-C28
 1.47 with sigma of 0.01
 N6-C29 = N6-C30 = N6-C31 = N6-C32
 1.47 with sigma of 0.01
 C4-O69 = C8-O90
 1.3 with sigma of 0.01
 C2-C3
 1.5 with sigma of 0.01
 C1-C2 \\sim C2-C3 \\sim C3-C4
 with sigma of 0.02
 C5-C6 \\sim C6-C7 \\sim C7-C8
 with sigma of 0.02
 C9-C10 \\sim C9-C11 \\sim C9-C12 \\sim C10-C11 \\sim C10-C12 \\sim C11-C12
 with sigma of 0.02
 C13-C14 \\sim C13-C15 \\sim C13-C16 \\sim C14-C15 \\sim C14-C16 \\sim C15-C16
 with sigma of 0.02
 C17-C18 \\sim C17-C19 \\sim C17-C20 \\sim C18-C19 \\sim C18-C20 \\sim C19-C20
 with sigma of 0.02
 C21-C22 \\sim C21-C23 \\sim C21-C24 \\sim C22-C23 \\sim C22-C24 \\sim C23-C24
 with sigma of 0.02
 C25-C26 \\sim C25-C27 \\sim C25-C28 \\sim C26-C27 \\sim C26-C28 \\sim C27-C28
 with sigma of 0.02
 C29-C30 \\sim C29-C31 \\sim C29-C32 \\sim C30-C31 \\sim C30-C32 \\sim C31-C32
 with sigma of 0.02
4. Rigid bond restraints
 C8, O90
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 W12, O63
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 W16, O54
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C5, C6
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O76, C1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
C8 \\sim O90: within 1.7A with sigma of 0.01 and sigma for terminal atoms of
0.02
Uanis(P2) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(P1) \\sim Ueq, Uanis(O2) \\sim Ueq, Uanis(O21) \\sim Ueq, Uanis(O64)
\\sim Ueq, Uanis(O75) \\sim Ueq, Uanis(O84) \\sim Ueq, Uanis(C19) \\sim Ueq,
Uanis(C26) \\sim Ueq: with sigma of 0.001 and sigma for terminal atoms of 0.002
Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3) \\sim Ueq, Uanis(C5) \\sim
Ueq, Uanis(C6) \\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C11)
\\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C14) \\sim Ueq,
Uanis(C15) \\sim Ueq, Uanis(C16) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C18)
\\sim Ueq, Uanis(C20) \\sim Ueq, Uanis(C21) \\sim Ueq, Uanis(C22) \\sim Ueq,
Uanis(C23) \\sim Ueq, Uanis(C27) \\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C30)
\\sim Ueq, Uanis(C31) \\sim Ueq, Uanis(C32) \\sim Ueq, Uanis(N1) \\sim Ueq,
Uanis(N2) \\sim Ueq, Uanis(N3) \\sim Ueq, Uanis(N4) \\sim Ueq, Uanis(N5) \\sim
Ueq, Uanis(N6) \\sim Ueq, Uanis(C28) \\sim Ueq, Uanis(C4) \\sim Ueq, Uanis(C8)
\\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O1) \\sim Ueq, Uanis(O3) \\sim Ueq, Uanis(O4) \\sim Ueq, Uanis(O6) \\sim
Ueq, Uanis(O7) \\sim Ueq, Uanis(O8) \\sim Ueq, Uanis(O9) \\sim Ueq, Uanis(O12)
\\sim Ueq, Uanis(O13) \\sim Ueq, Uanis(O14) \\sim Ueq, Uanis(O15) \\sim Ueq,
Uanis(O16) \\sim Ueq, Uanis(O17) \\sim Ueq, Uanis(O18) \\sim Ueq, Uanis(O20)
\\sim Ueq, Uanis(O24) \\sim Ueq, Uanis(O23) \\sim Ueq, Uanis(O25) \\sim Ueq,
Uanis(O26) \\sim Ueq, Uanis(O28) \\sim Ueq, Uanis(O29) \\sim Ueq, Uanis(O32)
\\sim Ueq, Uanis(O33) \\sim Ueq, Uanis(O34) \\sim Ueq, Uanis(O35) \\sim Ueq,
Uanis(O37) \\sim Ueq, Uanis(O40) \\sim Ueq, Uanis(O41) \\sim Ueq, Uanis(O43)
\\sim Ueq, Uanis(O45) \\sim Ueq, Uanis(O46) \\sim Ueq, Uanis(O47) \\sim Ueq,
Uanis(O51) \\sim Ueq, Uanis(O52) \\sim Ueq, Uanis(O53) \\sim Ueq, Uanis(O54)
\\sim Ueq, Uanis(O56) \\sim Ueq, Uanis(O59) \\sim Ueq, Uanis(O61) \\sim Ueq,
Uanis(O62) \\sim Ueq, Uanis(O63) \\sim Ueq, Uanis(O68) \\sim Ueq, Uanis(O66)
\\sim Ueq, Uanis(O69) \\sim Ueq, Uanis(O70) \\sim Ueq, Uanis(O71) \\sim Ueq,
Uanis(O73) \\sim Ueq, Uanis(O76) \\sim Ueq, Uanis(O77) \\sim Ueq, Uanis(O79)
\\sim Ueq, Uanis(O80) \\sim Ueq, Uanis(O81) \\sim Ueq, Uanis(O82) \\sim Ueq,
Uanis(O83) \\sim Ueq, Uanis(O85) \\sim Ueq, Uanis(O86) \\sim Ueq, Uanis(O87)
\\sim Ueq, Uanis(O88) \\sim Ueq, Uanis(O90) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
6. Others
 Fixed Uiso: C10(0.15232) C24(0.15938) C25(0.16997) O78(0.07224)
7.a Ternary CH refined with riding coordinates:
 C2(H2), C3(H3), C6(H6), C7(H7)
7.b Me refined with riding coordinates:
 C9(H9A,H9B,H9C), C10(H10A,H10B,H10C), C11(H11A,H11B,H11C), C12(H12A,H12B,
 H12C), C13(H13A,H13B,H13C), C14(H14A,H14B,H14C), C15(H15A,H15B,H15C), C16(H16A,
 H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C19(H19A,H19B,H19C),
 C20(H20A,H20B,H20C), C21(H21A,H21B,H21C), C22(H22A,H22B,H22C), C23(H23A,H23B,
 H23C), C24(H24A,H24B,H24C), C25(H25A,H25B,H25C), C26(H26A,H26B,H26C), C27(H27A,
 H27B,H27C), C28(H28A,H28B,H28C), C29(H29A,H29B,H29C), C30(H30A,H30B,H30C),
 C31(H31A,H31B,H31C), C32(H32A,H32B,H32C)
;
_smtbx_masks_special_details
;
A solvent mask was calculated and 2873.6 electrons were found in a volume of 5625.1\%A^3 in 4 voids. Three disordered K^+^ ions were determined by EDX measurement results. Therefore, this is consistent with the presence of 3[K]^+^ and 66[H2O] per formula unit which account for 2856.0 electrons.
;
_shelx_res_checksum              47316
_shelx_fab_checksum              81040
_olex2_submission_special_instructions 'No special instructions were received'