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_4003033
_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-Water
_space_group_crystal_system      orthorhombic
_space_group_IT_number           69
_space_group_name_Hall           '-F 2 2'
_space_group_name_H-M_alt        'F m m m'
_symmetry_space_group_name_Hall  '-F 2 2'
_symmetry_space_group_name_H-M   'F m m m'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2017-12-05
_audit_creation_method
;
Olex2 1.2
(compiled 2017.08.10 svn.r3458 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                   16.1063(7)
_cell_length_b                   28.5501(8)
_cell_length_c                   40.9518(9)
_cell_measurement_reflns_used    7903
_cell_measurement_temperature    150(2)
_cell_measurement_theta_max      65.0110
_cell_measurement_theta_min      5.3060
_cell_volume                     18831.1(11)
_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 0.977
_diffrn_measured_fraction_theta_max 0.977
_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    -74.00  31.00   1.00   80.00    --  -41.14  77.00 -60.00  105
  2  \w    -57.00 -21.00   1.00   80.00    --  -41.14 -38.00 120.00   36
  3  \w    109.00 154.00   1.00   90.00    --   89.96 125.00-150.00   45
  4  \w    128.00 162.00   1.00   90.00    --   89.96 125.00 -90.00   34
  5  \w      9.00  96.00   1.00   90.00    --   89.96 -95.00  30.00   87
  6  \w     67.00 131.00   1.00   90.00    --   89.96  61.00  60.00   64
;
_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      0.0328200000
_diffrn_orient_matrix_UB_12      0.0232260000
_diffrn_orient_matrix_UB_13      0.0221731000
_diffrn_orient_matrix_UB_21      -0.0056620000
_diffrn_orient_matrix_UB_22      -0.0116333000
_diffrn_orient_matrix_UB_23      0.0923518000
_diffrn_orient_matrix_UB_31      0.0175041000
_diffrn_orient_matrix_UB_32      -0.0472668000
_diffrn_orient_matrix_UB_33      -0.0117398000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54184
_diffrn_reflns_av_R_equivalents  0.0308
_diffrn_reflns_av_unetI/netI     0.0320
_diffrn_reflns_Laue_measured_fraction_full 0.977
_diffrn_reflns_Laue_measured_fraction_max 0.977
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -33
_diffrn_reflns_limit_l_max       43
_diffrn_reflns_limit_l_min       -47
_diffrn_reflns_number            10624
_diffrn_reflns_point_group_measured_fraction_full 0.977
_diffrn_reflns_point_group_measured_fraction_max 0.977
_diffrn_reflns_theta_full        65.225
_diffrn_reflns_theta_max         65.225
_diffrn_reflns_theta_min         3.330
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'SuperNova (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    3.001
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.27398
_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_colour_primary    colourless
_exptl_crystal_density_diffrn    0.854
_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
_platon_squeeze_details
;
TITL exp_2228_a.res in Pbca New: Cmca New: Fmmm
CELL   16.1063   28.5501   40.9518     90.00     90.00     90.00
SPGR Fmmm
C101 0.143 0.422 0.048 !       2.04 eA-3
C102 0.830 0.503 0.164 !       1.87 eA-3
C103 0.300 0.497 0.195 !       1.87 eA-3
C104 0.142 0.078 0.231 !       1.56 eA-3
C105 1.000 0.176 0.143 !       1.54 eA-3
C106 0.186 0.077 0.233 !       1.54 eA-3
C107 0.214 0.061 0.244 !       1.51 eA-3
C108 0.775 0.499 0.070 !       1.46 eA-3
C109 1.000 0.031 0.155 !       1.41 eA-3
C110 0.971 0.008 0.165 !       1.35 eA-3
Q111 0.057 0.148-0.003 !       1.35 eA-3
C112 0.500 0.404 0.194 !       1.34 eA-3
C113 0.300 0.237 0.049 !       1.32 eA-3
Q114 0.062 0.424 0.189 !       1.32 eA-3
C115 0.515 0.203 0.005 !       1.28 eA-3
C116 0.500 0.192 0.095 !       1.27 eA-3
C117 1.000 0.176 0.054 !       1.23 eA-3
C118 0.500 0.039-0.002 !       1.23 eA-3
C119 1.000 0.154 0.068 !       1.22 eA-3
C120 0.985 0.383 0.133 !       1.17 eA-3
Q121 0.743 0.031 0.001 !       1.15 eA-3
C122 0.500 0.042 0.023 !       1.14 eA-3
Q123 0.575 0.298 0.038 !       1.11 eA-3
C124 0.819 0.505 0.141 !       1.09 eA-3
Q125 0.774 0.358 0.155 !       1.08 eA-3
C126 0.590 0.154 0.047 !       1.07 eA-3
C127 0.611 0.178 0.054 !       1.05 eA-3
C128 1.000 0.066 0.185 !       1.01 eA-3
C129 0.749 0.187-0.003 !       1.00 eA-3
C130 0.122 0.307 0.046 !       0.99 eA-3
C131 0.470 0.056 0.227 !       0.98 eA-3
C132 0.127 0.457 0.110 !       0.98 eA-3
C133 0.373 0.543 0.390 !       0.98 eA-3
C134 0.112 0.060 0.615 !       0.95 eA-3
C135 0.719 0.164 0.003 !       0.94 eA-3
C136 0.533 0.291 0.104 !       0.92 eA-3
C137 0.035 0.422 0.156 !       0.90 eA-3
C138 1.000 0.377 0.106 !       0.89 eA-3
C139 0.856 0.257 0.066 !       0.87 eA-3
C140 0.782 0.496 0.195 !       0.87 eA-3
C141 0.454 0.045 0.246 !       0.86 eA-3
Q142 0.324 0.123 0.125 !       0.85 eA-3
Q143 0.173 0.337 0.204 !       0.84 eA-3
Q144 0.500 0.311 0.028 !       0.83 eA-3
C145 1.000 0.133 0.172 !       0.81 eA-3
C146 0.051 0.424 0.132 !       0.81 eA-3
Q147 0.812 0.203-0.002 !       0.81 eA-3
Q148 0.282 0.100 0.103 !       0.80 eA-3
C149 1.000 0.498 0.102 !       0.80 eA-3
Q150 0.500 0.499 0.047 !       0.80 eA-3
C151 0.868 0.480 0.102 !       0.79 eA-3
C152 0.112 0.282 0.063 !       0.79 eA-3
Q153 0.659 0.302 0.056 !       0.78 eA-3
C154 0.809 0.499 0.094 !       0.78 eA-3
Q155 0.123 0.049 0.007 !       0.77 eA-3
C156 0.500 0.275 0.102 !       0.77 eA-3
C157 0.500 0.161 0.100 !       0.77 eA-3
C158 0.465 0.023 0.110 !       0.76 eA-3
C159 0.500 0.234-0.004 !       0.76 eA-3
C160 0.808 0.341 0.033 !       0.76 eA-3
Q161 1.000 0.044 0.039 !       0.76 eA-3
C162 0.433 0.028 0.219 !       0.75 eA-3
C163 0.567 0.059 0.100 !       0.75 eA-3
Q164 0.801 0.468 0.031 !       0.73 eA-3
Q165 0.362 0.505 0.031 !       0.73 eA-3
C166 0.500 0.046 0.209 !       0.73 eA-3
Q167 0.778 0.086 0.000 !       0.73 eA-3
C168 0.938 0.499 0.211 !       0.72 eA-3
C169 0.809 0.457 0.062 !       0.72 eA-3
C170 1.000 0.502 0.203 !       0.71 eA-3
Q171 0.580 0.429 0.009 !       0.70 eA-3
C172 0.974 0.502 0.078 !       0.70 eA-3
C173 0.846 0.482 0.116 !       0.69 eA-3
C174 0.371 0.017 0.133 !       0.69 eA-3
C175 0.796 0.469 0.102 !       0.68 eA-3
C176 0.044 0.056 0.196 !       0.68 eA-3
C177 0.500 0.286 0.056 !       0.67 eA-3
C178 0.500 0.414 0.165 !       0.66 eA-3
Q179 0.924 0.277 0.118 !       0.66 eA-3
C180 0.776 0.501 0.109 !       0.65 eA-3
Q181 0.500 0.421 0.034 !       0.63 eA-3
C182 0.464 0.017 0.229 !       0.62 eA-3
Q183 0.401 0.500 0.055 !       0.62 eA-3
C184 0.500 0.044 0.069 !       0.62 eA-3
Q185 0.654 0.299 0.022 !       0.62 eA-3
C186 0.682 0.148 0.001 !       0.61 eA-3
Q187 0.857 0.125-0.001 !       0.61 eA-3
Q188 0.124 0.188-0.001 !       0.61 eA-3
C189 1.000 0.503 0.125 !       0.61 eA-3
C190 0.342 0.125 0.046 !       0.60 eA-3
C191 0.869 0.495 0.055 !       0.60 eA-3
C192 1.000 0.428 0.048 !       0.60 eA-3
C193 0.935 0.500 0.125 !       0.59 eA-3
C194 0.831 0.502 0.211 !       0.59 eA-3
Q195 0.616 0.297 0.008 !       0.59 eA-3
C196 0.451 0.501 0.203 !       0.58 eA-3
Q197 1.000 0.078-0.001 !       0.58 eA-3
Q198 0.215 0.156-0.001 !       0.57 eA-3
C199 0.500 0.007 0.063 !       0.57 eA-3
;
_refine_diff_density_max         0.929
_refine_diff_density_min         -2.031
_refine_diff_density_rms         0.114
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.042
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     187
_refine_ls_number_reflns         4244
_refine_ls_number_restraints     284
_refine_ls_restrained_S_all      1.109
_refine_ls_R_factor_all          0.0772
_refine_ls_R_factor_gt           0.0730
_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^)+(0.1076P)^2^+317.9772P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1992
_refine_ls_wR_factor_ref         0.2035
_reflns_Friedel_coverage         0.000
_reflns_number_gt                3845
_reflns_number_total             4244
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            LIFM-114-Water-solved.cif
_cod_data_source_block           LIFM-114-Water
_cod_database_code               4003033
_shelx_shelxl_version_number     2014/7
_shelx_estimated_absorpt_t_max   0.753
_shelx_estimated_absorpt_t_min   0.466
_reflns_odcompleteness_completeness 99.80
_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 = C11-C12A = C12A-C13A = C13A-C8
 1.39 with sigma of 0.01
 C8-C10A = C9A-C11 = C10A-C12A = C11-C13A = C12A-C8 = C13A-C9A
 2.4 with sigma of 0.01
 C9A-C12A = C10A-C13A
 2.8 with sigma of 0.01
3. Restrained planarity
 C8, C9A, C10A, C11, C12A, C13A
 with sigma of 0.01
4. Rigid bond restraints
 C2, C3, C4, C5, C6, C7
 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
 O1, O2, C1
 with sigma for 1-2 distances of 0.01 and sigma for 1-3 distances of 0.01
 Zr2, O3, O4, O2
 with sigma for 1-2 distances of 0.005 and sigma for 1-3 distances of 0.005
5. Uiso/Uaniso restraints and constraints
O1 \\sim O2 \\sim C1: within 2A with sigma of 0.04 and sigma for terminal atoms
of 0.08
C2 \\sim C3 \\sim C4 \\sim C5 \\sim C6 \\sim C7: 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
Zr2 \\sim O3 \\sim O4 \\sim O2: within 2A with sigma of 0.005 and sigma for
terminal atoms of 0.02
Uanis(O5) \\sim Ueq, Uanis(O6) \\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(O1) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms
of 0.02
6. Others
 Fixed Sof: C9(0.5) H9(0.5) C10(0.5) H10(0.5) C12(0.5) H12(0.5) C13(0.5)
 H13(0.5) C9A(0.5) H9A(0.5) C10A(0.5) H10A(0.5) C12A(0.5) H12A(0.5) C13A(0.5)
 H13A(0.5)
7.a Aromatic/amide H refined with riding coordinates:
 C3(H3), C4(H4), C6(H6), C7(H7), C9(H9), C10(H10), C12(H12), C13(H13),
 C9A(H9A), C10A(H10A), C12A(H12A), C13A(H13A)
7.b Fitted hexagon refined as free rotating group:
 C2(C3,C4,C5,C6,C7), C8(C9,C10,C11,C12,C13)
;
_platon_squeeze_void_probe_radius 1.20
_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 2.829
_oxdiff_exptl_absorpt_empirical_full_min 0.693