All Roads Lead to Rome: Tuning the Luminescence of a Breathing Catenated Zr-MOF by Programmable Multiplexing Pathways
Chen, Cheng-Xia; Wei, Zhang-Wen; Cao, Chen-Chen; Yin, Shao-Yun; Qiu, Qian-Feng; Zhu, Neng-Xiu; Xiong, Yang-Yang; Jiang, Ji-Jun; Pan, Mei; Su, Cheng-Yong; Chemistry of Materials 31 (2019) 5550–; doi:10.1021/acs.chemmater.9b01258

data_4003034
_publ_section_title
;
 All Roads Lead to Rome: Tuning the Luminescence of a Breathing Catenated
 Zr-MOF by Programmable Multiplexing Pathways
;
_journal_issue                   15
_journal_name_full               'Chemistry of Materials'
_journal_page_first              5550
_journal_paper_doi               10.1021/acs.chemmater.9b01258
_journal_volume                  31
_journal_year                    2019
_chemical_formula_moiety         'C108 H64 O32 Zr6 [+ solvent]'
_chemical_formula_sum            'C108 H64 O32 Zr6'
_chemical_formula_weight         2420.91
_chemical_name_common            LIFM-114-DCM
_space_group_crystal_system      orthorhombic
_space_group_IT_number           65
_space_group_name_Hall           '-C 2 2'
_space_group_name_H-M_alt        'C m m m'
_symmetry_space_group_name_Hall  '-C 2 2'
_symmetry_space_group_name_H-M   'C m m m'
_atom_sites_solution_hydrogens   mixed
_audit_creation_date             2017-12-03
_audit_creation_method
;
Olex2 1.2
(compiled 2017.03.02 svn.r3394 for OlexSys, GUI svn.r5381)
;
_cell_angle_alpha                90
_cell_angle_beta                 90
_cell_angle_gamma                90
_cell_formula_units_Z            4
_cell_length_a                   21.4419(8)
_cell_length_b                   42.3169(10)
_cell_length_c                   17.9262(5)
_cell_measurement_reflns_used    5477
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      65.2890
_cell_measurement_theta_min      4.4750
_cell_volume                     16265.4(8)
_computing_cell_refinement       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_collection       'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_data_reduction        'CrysAlisPro 1.171.38.43 (Rigaku OD, 2015)'
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      150(2)
_diffrn_detector                 'CCD plate'
_diffrn_detector_area_resol_mean 10.6525
_diffrn_detector_type            Atlas
_diffrn_measured_fraction_theta_full 0.979
_diffrn_measured_fraction_theta_max 0.979
_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    -82.00  34.00   1.00  150.00    --  -41.14  19.00 -60.00  116
  2  \w    108.00 160.00   1.00  140.00    --   89.96 125.00-180.00   52
  3  \w     30.00  56.00   1.00  140.00    --   89.96 -30.00-150.00   26
  4  \w     82.00 110.00   1.00  140.00    --   89.96 -30.00-150.00   28
  5  \w     96.00 163.00   1.00  140.00    --   89.96 125.00   0.00   67
  6  \w     78.00 158.00   1.00  140.00    --   89.96  61.00-180.00   80
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'SuperNova, Dual, Cu at zero, Atlas'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0013912000
_diffrn_orient_matrix_UB_12      0.0349778000
_diffrn_orient_matrix_UB_13      0.0236386000
_diffrn_orient_matrix_UB_21      -0.0396092000
_diffrn_orient_matrix_UB_22      -0.0087532000
_diffrn_orient_matrix_UB_23      0.0687319000
_diffrn_orient_matrix_UB_31      0.0598639000
_diffrn_orient_matrix_UB_32      -0.0050207000
_diffrn_orient_matrix_UB_33      0.0459879000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0414
_diffrn_reflns_av_unetI/netI     0.0408
_diffrn_reflns_Laue_measured_fraction_full 0.979
_diffrn_reflns_Laue_measured_fraction_max 0.979
_diffrn_reflns_limit_h_max       24
_diffrn_reflns_limit_h_min       -14
_diffrn_reflns_limit_k_max       48
_diffrn_reflns_limit_k_min       -34
_diffrn_reflns_limit_l_max       20
_diffrn_reflns_limit_l_min       -18
_diffrn_reflns_number            18939
_diffrn_reflns_point_group_measured_fraction_full 0.979
_diffrn_reflns_point_group_measured_fraction_max 0.979
_diffrn_reflns_theta_full        65.353
_diffrn_reflns_theta_max         65.353
_diffrn_reflns_theta_min         3.751
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.474
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.57141
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.38.43 (Rigaku Oxford Diffraction, 2015)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            Colourless
_exptl_crystal_density_diffrn    0.989
_exptl_crystal_description       Rod
_exptl_crystal_F_000             4832
_exptl_crystal_size_max          0.3
_exptl_crystal_size_mid          0.1
_exptl_crystal_size_min          0.1
_refine_diff_density_max         1.475
_refine_diff_density_min         -4.000
_refine_diff_density_rms         0.201
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.692
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     481
_refine_ls_number_reflns         7377
_refine_ls_number_restraints     643
_refine_ls_restrained_S_all      1.722
_refine_ls_R_factor_all          0.1428
_refine_ls_R_factor_gt           0.1295
_refine_ls_shift/su_max          0.000
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.2000P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.3874
_refine_ls_wR_factor_ref         0.4043
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5708
_reflns_number_total             7377
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            LIFM-114-DCM-solved.cif
_cod_data_source_block           LIFM-114-DCM
_cod_database_code               4003034
_shelx_shelxl_version_number     2014/7
_reflns_odcompleteness_completeness 99.81
_reflns_odcompleteness_iscentric 1
_reflns_odcompleteness_theta     61.08
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups
2. Restrained distances
 C8-C9A = C9A-C10A = C10A-C11
 1.39 with sigma of 0.01
 C11-C12A = C12A-C13A = C13A-C8
 1.39 with sigma of 0.01
 C8-C10A = C9A-C11 = C10A-C12A
 2.4 with sigma of 0.01
 C11-C13A = C12A-C8 = C13A-C9A
 2.4 with sigma of 0.01
 C9A-C12A = C10A-C13A
 2.8 with sigma of 0.01
 C15-C16 = C19-C22 = C25-C28
 1.49 with sigma of 0.01
 C15A-C16A = C19A-C22A = C25A-C29
 1.49 with sigma of 0.01
 C28-C29
 1.41 with sigma of 0.01
 C15-O3 = C15-O4 = C15A-O3A = C15A-O4A
 1.29 with sigma of 0.01
 Zr3-O9 = Zr4-O9 = Zr5-O9
 2.15 with sigma of 0.02
 Zr3-O14 = Zr4-O14
 2.15 with sigma of 0.02
 Zr3-O3
 2.094 with sigma of 0.01
 Zr4-O4
 2.127 with sigma of 0.01
 Zr3_$1-O3A
 2.105 with sigma of 0.01
 Zr5_$1-O4A
 2.138 with sigma of 0.01
 O14-O14A
 1.681 with sigma of 0.01
 O11-O12 = O10-O11 = O12-O13
 3.2 with sigma of 0.01
 Zr3-O14A
 1.264 with sigma of 0.01
 Zr4-O10 = Zr4-O11 = Zr5-O12 = Zr5-O13
 2.25 with sigma of 0.02
3. Restrained planarity
 C8, C9A, C10A, C11, C12A, C13A
 with sigma of 0.01
4. Rigid bond restraints
 Zr3, Zr4, Zr5, O9, O10, O11, O12, O13, O14, O14A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 O3, O4, C15, C16, C17, C18, C19, C20, C21, C22, C23, C24, C25, C26, C27, C28,
 C29, C15A, C16A, C17A, C18A, C19A, C20A, C21A, C22A, C23A, C24A, C25A, C26A,
 C27A, O3A, O4A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 C8, C9, C10, C11, C12, C13, C9A, C10A, C12A, C13A
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Zr1, Zr2, O1, O2, O5, O6, O7, O8
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
5. Uiso/Uaniso restraints and constraints
Zr3 \\sim Zr4 \\sim Zr5 \\sim O9 \\sim O10 \\sim O11 \\sim O12 \\sim O13 \\sim
O14 \\sim O14A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
O3 \\sim O4 \\sim C15 \\sim C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim
C21 \\sim C22 \\sim C23 \\sim C24 \\sim C25 \\sim C26 \\sim C27 \\sim C28 \\sim
C29 \\sim C15A \\sim C16A \\sim C17A \\sim C18A \\sim C19A \\sim C20A \\sim
C21A \\sim C22A \\sim C23A \\sim C24A \\sim C25A \\sim C26A \\sim C27A \\sim
O3A \\sim O4A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
C8 \\sim C9 \\sim C10 \\sim C11 \\sim C12 \\sim C13 \\sim C9A \\sim C10A \\sim
C12A \\sim C13A: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02
Zr1 \\sim Zr2 \\sim O1 \\sim O2 \\sim O5 \\sim O6 \\sim O7 \\sim O8: within 2A
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O13) \\sim Ueq, Uanis(C1) \\sim Ueq, Uanis(C2) \\sim Ueq, Uanis(C3) \\sim
Ueq, Uanis(C4) \\sim Ueq, Uanis(C5) \\sim Ueq, Uanis(C6) \\sim Ueq, Uanis(C7)
\\sim Ueq, Uanis(C8) \\sim Ueq, Uanis(C9) \\sim Ueq, Uanis(C10) \\sim Ueq,
Uanis(C11) \\sim Ueq, Uanis(C12) \\sim Ueq, Uanis(C13) \\sim Ueq, Uanis(C14)
\\sim Ueq, Uanis(O5) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms
of 0.02
Uanis(O8) \\sim Ueq: with sigma of 0.002 and sigma for terminal atoms of 0.01
6. Others
 Fixed Sof: Zr3(0.25) Zr4(0.25) Zr5(0.25) O3(0.5) O4(0.5) O9(0.5) O10(0.25)
 O11(0.25) O12(0.25) O13(0.25) O14(0.25) C9(0.5) H9(0.5) C10(0.5) H10(0.5)
 C12(0.5) H12(0.5) C13(0.5) H13(0.5) C15(0.5) C16(0.5) C17(0.5) H17(0.5)
 C18(0.5) H18(0.5) C19(0.5) C20(0.5) H20(0.5) C21(0.5) H21(0.5) C22(0.5)
 C23(0.5) H23(0.5) C24(0.5) H24(0.5) C25(0.5) C26(0.5) H26(0.5) C27(0.5)
 H27(0.5) C29(0.25) O3A(0.5) O4A(0.5) O14A(0.25) C9A(0.5) H9A(0.5) C10A(0.5)
 H10A(0.5) C12A(0.5) H12A(0.5) C13A(0.5) H13A(0.5) C15A(0.5) C16A(0.5)
 C17A(0.5) H17A(0.5) C18A(0.5) H18A(0.5) C19A(0.5) C20A(0.5) H20A(0.5)
 C21A(0.5) H21A(0.5) C22A(0.5) C23A(0.5) H23A(0.5) C24A(0.5) H24A(0.5)
 C25A(0.5) C26A(0.5) H26A(0.5) C27A(0.5) H27A(0.5)
7.a Riding coordinates:
 C24(H24), C26(H26), C24A(H24A), C26A(H26A)
7.b Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C9(H9), C10(H10), C12(H12), C13(H13),
 C17(H17), C18(H18), C20(H20), C21(H21), C23(H23), C27(H27), C9A(H9A),
 C10A(H10A), C12A(H12A), C13A(H13A), C17A(H17A), C18A(H18A), C20A(H20A),
 C21A(H21A), C23A(H23A), C27A(H27A)
7.c Fitted hexagon refined as free rotating group:
 C2(C3,C4,C5,C6,C7), C8(C9,C10,C11,C12,C13), C16(C17,C18,C19,C20,C21), C22(C23,
 C24,C25,C26,C27), C16A(C17A,C18A,C19A,C20A,C21A), C22A(C23A,C24A,C25A,C26A,
 C27A)
;
_shelx_res_checksum              99784
_shelx_hkl_checksum              27956
_shelx_fab_checksum              42116
_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
- Detector area scaling
;
_oxdiff_exptl_absorpt_empirical_full_max 1.969
_oxdiff_exptl_absorpt_empirical_full_min 0.657