Novel "Turn-Off" and "Turn-On" Fluorescent Responses for Zr⁴⁺ Enabled by Rare-Earth Coordination Polymers Based on the 2,5-Dihydroxyterephthalic Acid ligand
Liu, Yan; Chen, Wanting; Zheng, Bobi; Xu, Han; Tian, Jumei; Dalton Transactions  (2026) –; doi:10.1039/D5DT02864G

data_7720831
_publ_section_title
;
 Novel "turn-off" and "turn-on" fluorescent responses for Zr<sup>4+</sup>
 enabled by rare-earth coordination polymers based on the
 2,5-dihydroxyterephthalic acid ligand.
;
_journal_issue                   18
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              7251
_journal_page_last               7259
_journal_paper_doi               10.1039/d5dt02864g
_journal_volume                  55
_journal_year                    2026
_chemical_formula_moiety         'C30 H34 N2 O24 Y2, 2(C3 H7 N O), H2 O'
_chemical_formula_sum            'C36 H50 N4 O27 Y2'
_chemical_formula_weight         1148.62
_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   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2023-04-15
_audit_creation_method
;
Olex2 1.5
(compiled 2023.03.06 svn.rbb2c1857 for OlexSys, GUI svn.r6748)
;
_audit_update_record
;
2023-12-06 deposited with the CCDC.	2026-04-06 downloaded from the CCDC.
;
_cell_angle_alpha                83.590(2)
_cell_angle_beta                 83.845(2)
_cell_angle_gamma                79.622(2)
_cell_formula_units_Z            2
_cell_length_a                   10.7730(2)
_cell_length_b                   11.2540(2)
_cell_length_c                   19.6698(4)
_cell_measurement_reflns_used    23124
_cell_measurement_temperature    233.01(10)
_cell_measurement_theta_max      76.2810
_cell_measurement_theta_min      3.9950
_cell_volume                     2321.80(8)
_computing_cell_refinement       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.41.123a (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      233.01(10)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.4741
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.978
_diffrn_measurement_details
;
List of Runs (angles in degrees, time in seconds):

  # Type    Start    End  Width  t~exp~   \w     \q     \k     \f   Frames
  1  \w    -57.00  29.00   1.00    1.00    --  -40.50  77.00  30.00   86
  2  \w    -49.00  34.00   1.00    1.00    --  -40.50  19.00 -90.00   83
  3  \w    -63.00  30.00   1.00    1.00    --  -40.50  37.00-180.00   93
  4  \w    -77.00  -7.00   1.00    1.00    --  -40.50  19.00  30.00   70
  5  \w     11.00  41.00   1.00    1.00    --   43.04  80.00  -2.07   30
  6  \w     22.00  79.00   1.00    1.00    --   43.04  37.00  60.00   57
  7  \w     12.00  42.00   1.00    1.00    --   43.04  80.00-156.76   30
  8  \w     16.00  50.00   1.00    1.00    --   43.04  57.00  90.00   34
  9  \w     41.00  98.00   1.00    1.00    --   43.04-125.00 -90.00   57
 10  \w     57.00 105.00   1.00    1.00    --   43.04  57.00-180.00   48
 11  \w     16.00  54.00   1.00    1.00    --   43.04  57.00-180.00   38
 12  \w     58.00 100.00   1.00    1.00    --   43.04  57.00  90.00   42
 13  \w     11.00  36.00   1.00    1.00    --   43.04  78.00 -77.69   25
 14  \w     12.00  40.00   1.00    1.00    --   43.04  79.00 116.86   28
 15  \w     15.00  42.00   1.00    1.00    --   43.04  77.00  29.60   27
 16  \w     28.00  76.00   1.00    1.00    --   43.04  57.00 -30.00   48
 17  \w     16.00 106.00   1.00    1.00    --   43.04  57.00 -90.00   90
 18  \w     81.00 107.00   1.00    1.00    --  111.00  70.00  52.28   26
 19  \w     83.00 112.00   1.00    1.00    --  111.00  64.00   7.71   29
 20  \w     86.00 131.00   1.00    1.00    --  111.00  55.00  44.35   45
 21  \w     85.00 171.00   1.00    1.00    --  111.00  57.00 -42.72   86
 22  \w     83.00 109.00   1.00    1.00    --  111.00  61.00  30.00   26
 23  \w     88.00 160.00   1.00    1.00    --  111.00  45.00-150.00   72
 24  \w     86.00 112.00   1.00    1.00    --  111.00  50.00  85.74   26
 25  \w     84.00 111.00   1.00    1.00    --  111.00  57.00 142.88   27
 26  \w     87.00 167.00   1.00    1.00    --  111.00  45.00 -60.00   80
 27  \w    140.00 166.00   1.00    1.00    --  111.00  53.00  94.80   26
 28  \w     41.00 139.00   1.00    1.00    --  111.00 -61.00  90.00   98
 29  \w     83.00 109.00   1.00    1.00    --  111.00  61.00-150.00   26
 30  \w     78.00 105.00   1.00    1.00    --  111.00 -94.00 -30.00   27
 31  \w     76.00 107.00   1.00    1.00    --  111.00 -94.00 150.00   31
 32  \w     84.00 175.00   1.00    1.00    --  111.00  57.00-127.89   91
 33  \w     83.00 109.00   1.00    1.00    --  111.00  61.00   0.00   26
 34  \w     44.00 106.00   1.00    1.00    --  111.00 -94.00-120.00   62
 35  \w     84.00 111.00   1.00    1.00    --  111.00  57.00 116.97   27
 36  \w     86.00 178.00   1.00    1.00    --  111.00  51.00  -8.44   92
 37  \w     87.00 177.00   1.00    1.00    --  111.00  45.00 120.00   90
 38  \w     84.00 109.00   1.00    1.00    --  111.00  61.00-180.00   25
 39  \w     83.00 109.00   1.00    1.00    --  111.00  61.00 -90.00   26
 40  \w     83.00 109.00   1.00    1.00    --  111.00  61.00 120.00   26
 41  \w     81.00 156.00   1.00    1.00    --  111.00  70.00 159.06   75
 42  \w     83.00 109.00   1.00    1.00    --  111.00  61.00 150.00   26
 43  \w     83.00 109.00   1.00    1.00    --  111.00  61.00 -30.00   26
 44  \w     84.00 109.00   1.00    1.00    --  111.00  61.00 -60.00   25
 45  \w    152.00 177.00   1.00    1.00    --  111.00  61.00-120.00   25
 46  \w     34.00 108.00   1.00    1.00    --  111.00-105.00  83.30   74
 47  \w     83.00 109.00   1.00    1.00    --  111.00  61.00-120.00   26
 48  \w     42.00 138.00   1.00    1.00    --  111.00 -61.00 -90.00   96
 49  \w    132.00 175.00   1.00    1.00    --  111.00  70.00  52.28   43
 50  \w    133.00 175.00   1.00    1.00    --  111.00  61.00  30.00   42
 51  \w     85.00 110.00   1.00    1.00    --  111.00  59.00-101.33   25
 52  \w     84.00 110.00   1.00    1.00    --  111.00  57.00  -1.72   26
 53  \w     85.00 119.00   1.00    1.00    --  111.00  53.00  94.80   34
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at home/near, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.1253333000
_diffrn_orient_matrix_UB_12      0.0382121000
_diffrn_orient_matrix_UB_13      0.0125510000
_diffrn_orient_matrix_UB_21      -0.0105778000
_diffrn_orient_matrix_UB_22      -0.0603156000
_diffrn_orient_matrix_UB_23      0.0741710000
_diffrn_orient_matrix_UB_31      0.0740578000
_diffrn_orient_matrix_UB_32      -0.1201810000
_diffrn_orient_matrix_UB_33      -0.0245451000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0293
_diffrn_reflns_av_unetI/netI     0.0262
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.978
_diffrn_reflns_limit_h_max       13
_diffrn_reflns_limit_h_min       -13
_diffrn_reflns_limit_k_max       13
_diffrn_reflns_limit_k_min       -14
_diffrn_reflns_limit_l_max       24
_diffrn_reflns_limit_l_min       -24
_diffrn_reflns_number            36639
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.978
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         76.239
_diffrn_reflns_theta_min         4.011
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    4.201
_exptl_absorpt_correction_T_max  0.627
_exptl_absorpt_correction_T_min  0.453
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.123a (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.643
_exptl_crystal_description       block
_exptl_crystal_F_000             1176
_exptl_crystal_size_max          0.304
_exptl_crystal_size_mid          0.185
_exptl_crystal_size_min          0.111
_refine_diff_density_max         1.209
_refine_diff_density_min         -0.501
_refine_diff_density_rms         0.071
_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     828
_refine_ls_number_reflns         9735
_refine_ls_number_restraints     599
_refine_ls_restrained_S_all      1.041
_refine_ls_R_factor_all          0.0330
_refine_ls_R_factor_gt           0.0274
_refine_ls_shift/su_max          0.004
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.0323P)^2^+2.0190P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.0663
_refine_ls_wR_factor_ref         0.0693
_reflns_Friedel_coverage         0.000
_reflns_number_gt                8509
_reflns_number_total             9517
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt02864g2.cif
_cod_data_source_block           2
_cod_depositor_comments
'Adding full bibliography for 7720830--7720831.cif.'
_cod_database_code               7720831
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.653
_shelx_estimated_absorpt_t_min   0.362
_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, All O(H) groups, All O(H,H) groups
2. Restrained distances
 N3A-C32A
 1.45 with sigma of 0.02
 C31A-O22A
 1.22 with sigma of 0.02
 C31A-N3A
 1.36 with sigma of 0.02
 N3A-C33A
 1.46 with sigma of 0.02
 C31A-C32A
 2.46 with sigma of 0.04
 C31A-C33A
 2.45 with sigma of 0.01
 C33A-C32A
 2.45 with sigma of 0.01
 O20-C25 \\sim O20-C25A
 with sigma of 0.02
 N1-C25 \\sim N1A-C25A
 with sigma of 0.02
 N3A-C32A \\sim N3A-C33A
 with sigma of 0.02
 N1-C27 \\sim N1A-C27A
 with sigma of 0.02
 N1-C26 \\sim N1A-C26A
 with sigma of 0.02
 O20-N1 \\sim O20-N1A
 with sigma of 0.04
 C25-C27 \\sim C25A-C27A
 with sigma of 0.04
 C25-C26 \\sim C25A-C26A
 with sigma of 0.04
 C36-C34 \\sim C36A-C34A
 with sigma of 0.04
 C27-C26 \\sim C27A-C26A
 with sigma of 0.04
 O19-C28 \\sim O19-C28A
 with sigma of 0.02
 N2-C28 \\sim N2A-C28A
 with sigma of 0.02
 N2-C29 \\sim N2A-C29A
 with sigma of 0.02
 N2-C30 \\sim N2A-C30A
 with sigma of 0.02
 O19-N2 \\sim O19-N2A
 with sigma of 0.04
 C28-C29 \\sim C28A-C29A
 with sigma of 0.04
 C28-C30 \\sim C28A-C30A
 with sigma of 0.04
 C29-C30 \\sim C29A-C30A
 with sigma of 0.04
 O21-C35 \\sim O21A-C35A
 with sigma of 0.02
 N4-C35 \\sim N4A-C35A
 with sigma of 0.02
 N4-C36 \\sim N4A-C36A
 with sigma of 0.02
 O12-C11 \\sim O12A-C11
 with sigma of 0.02
 N4-C34 \\sim N4A-C34A
 with sigma of 0.02
 O21-N4 \\sim O21A-N4A
 with sigma of 0.04
 C35-C36 \\sim C35A-C36A
 with sigma of 0.04
 C35-C34 \\sim C35A-C34A
 with sigma of 0.04
3. Restrained planarity
 C31A, O22A, N3A, C32A, C33A
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
N3 \\sim O22 \\sim C31 \\sim C33 \\sim C32: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C31A \\sim O22A \\sim N3A \\sim C32A \\sim C33A: within 2A with sigma of 0.04
and sigma for terminal atoms of 0.08 within 2A
O21 \\sim N4 \\sim C35 \\sim C36 \\sim C34 \\sim N4A \\sim O21A \\sim C35A
\\sim C36A \\sim C34A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
O12 \\sim C11 \\sim O12A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
N1 \\sim C25 \\sim C27 \\sim C26 \\sim C25A \\sim N1A \\sim C26A \\sim C27A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
N2 \\sim C28 \\sim C29 \\sim C30 \\sim C28A \\sim N2A \\sim C29A \\sim C30A:
within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
O22 \\sim N3 \\sim C31 \\sim C33 \\sim C32 \\sim C31A \\sim O22A \\sim N3A
\\sim C32A \\sim C33A: within 2A with sigma of 0.01 and sigma for terminal
atoms of 0.02 within 2A
Uanis(C29) \\sim Ueq, Uanis(C29A) \\sim Ueq: with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(C28) \\sim Ueq, Uanis(C28A) \\sim Ueq, Uanis(C30) \\sim Ueq, Uanis(C30A)
\\sim Ueq, Uanis(C29) \\sim Ueq, Uanis(C29A) \\sim Ueq, Uanis(C26A) \\sim Ueq,
Uanis(C26) \\sim Ueq, Uanis(C27A) \\sim Ueq, Uanis(C27) \\sim Ueq: with sigma
of 0.005 and sigma for terminal atoms of 0.01
5. Rigid body (RIGU) restrains
 C31A, O22A, N3A, C32A, C33A
 with sigma for 1-2 distances of 0.004 and sigma for 1-3 distances of 0.004
6. Others
 Sof(C25A)=Sof(H25A)=Sof(N1A)=Sof(C26A)=Sof(H26D)=Sof(H26E)=Sof(H26F)=
 Sof(C27A)=Sof(H27D)=Sof(H27E)=Sof(H27F)=1-FVAR(1)
 Sof(N1)=Sof(C25)=Sof(H25)=Sof(C27)=Sof(H27A)=Sof(H27B)=Sof(H27C)=Sof(C26)=
 Sof(H26A)=Sof(H26B)=Sof(H26C)=FVAR(1)
 Sof(C28A)=Sof(H28A)=Sof(N2A)=Sof(C29A)=Sof(H29D)=Sof(H29E)=Sof(H29F)=
 Sof(C30A)=Sof(H30D)=Sof(H30E)=Sof(H30F)=1-FVAR(2)
 Sof(N2)=Sof(C28)=Sof(H28)=Sof(C29)=Sof(H29A)=Sof(H29B)=Sof(H29C)=Sof(C30)=
 Sof(H30A)=Sof(H30B)=Sof(H30C)=FVAR(2)
 Sof(N4A)=Sof(O21A)=Sof(C35A)=Sof(H35A)=Sof(C36A)=Sof(H36D)=Sof(H36E)=
 Sof(H36F)=Sof(C34A)=Sof(H34D)=Sof(H34E)=Sof(H34F)=1-FVAR(3)
 Sof(O21)=Sof(N4)=Sof(C35)=Sof(H35)=Sof(C36)=Sof(H36A)=Sof(H36B)=Sof(H36C)=
 Sof(C34)=Sof(H34A)=Sof(H34B)=Sof(H34C)=FVAR(3)
 Sof(O12A)=Sof(H12B)=1-FVAR(4)
 Sof(O12)=Sof(H12)=FVAR(4)
 Sof(C31A)=Sof(H31A)=Sof(O22A)=Sof(N3A)=Sof(C32A)=Sof(H32D)=Sof(H32E)=
 Sof(H32F)=Sof(C33A)=Sof(H33D)=Sof(H33E)=Sof(H33F)=1-FVAR(5)
 Sof(N3)=Sof(O22)=Sof(C31)=Sof(H31)=Sof(C33)=Sof(H33A)=Sof(H33B)=Sof(H33C)=
 Sof(C32)=Sof(H32A)=Sof(H32B)=Sof(H32C)=FVAR(5)
7.a Free rotating group:
 O5W(H5WA,H5WB)
7.b Rotating group:
 O1W(H1WA,H1WB), O2W(H2WA,H2WB), O4W(H4WA,H4WB), O3W(H3WA,H3WB)
7.c Aromatic/amide H refined with riding coordinates:
 C7(H7), C15(H15), C4(H4A), C23(H23), C35(H35), C12(H12A), C19(H19), C28(H28),
 C25(H25), C31(H31), C25A(H25A), C28A(H28A), C35A(H35A), C31A(H31A)
7.d Idealised Me refined as rotating group:
 C36(H36A,H36B,H36C), C33(H33A,H33B,H33C), C29(H29A,H29B,H29C), C27(H27A,H27B,
 H27C), C30(H30A,H30B,H30C), C34(H34A,H34B,H34C), C26(H26A,H26B,H26C), C32(H32A,
 H32B,H32C), C26A(H26D,H26E,H26F), C27A(H27D,H27E,H27F), C29A(H29D,H29E,H29F),
 C30A(H30D,H30E,H30F), C36A(H36D,H36E,H36F), C34A(H34D,H34E,H34F), C32A(H32D,
 H32E,H32F), C33A(H33D,H33E,H33F)
7.e Idealised tetrahedral OH refined as rotating group:
 O4(H4), O3(H3), O13(H13), O9(H9), O12(H12), O18(H18), O12A(H12B)
;
_shelx_res_checksum              40839
_olex2_submission_special_instructions 'No special instructions were received'
_oxdiff_exptl_absorpt_empirical_details
;
Empirical correction (ABSPACK) includes:
- Absorption correction using spherical harmonics
- Frame scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.295
_oxdiff_exptl_absorpt_empirical_full_min 0.831