Tuning phase transition and fluorescence quenching in 0D organic-inorganic hybrid materials by precise organic cation modification.
Chen, Leqi; Zhou, Zining; Yang, Yawen; Ye, Qiong; Dalton transactions (Cambridge, England : 2003) 54 (2025) 5560–5567; doi:10.1039/d5dt00057b

data_7718286
_publ_section_title
;
 Tuning phase transition and fluorescence quenching in 0D
 organic-inorganic hybrid materials by precise organic cation
 modification.
;
_journal_issue                   13
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              5560
_journal_page_last               5567
_journal_paper_doi               10.1039/d5dt00057b
_journal_volume                  54
_journal_year                    2025
_chemical_formula_moiety         'Br4 Mn, 2(C5 H14 P)'
_chemical_formula_sum            'C10 H28 Br4 Mn P2'
_chemical_formula_weight         584.84
_space_group_crystal_system      monoclinic
_space_group_IT_number           14
_space_group_name_Hall           '-P 2ybc'
_space_group_name_H-M_alt        'P 1 21/c 1'
_atom_sites_solution_hydrogens   geom
_atom_sites_solution_primary     dual
_atom_sites_solution_secondary   difmap
_audit_creation_date             2025-02-14
_audit_creation_method
;
Olex2 1.5
(compiled 2022.04.07 svn.rca3783a0 for OlexSys, GUI svn.r6498)
;
_audit_update_record
;
2025-02-14 deposited with the CCDC.	2025-02-28 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 117.916(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   18.5525(3)
_cell_length_b                   14.0694(2)
_cell_length_c                   18.3426(2)
_cell_measurement_reflns_used    27721
_cell_measurement_temperature    100.00(17)
_cell_measurement_theta_max      71.5410
_cell_measurement_theta_min      4.1220
_cell_volume                     4230.70(13)
_computing_cell_refinement       'CrysAlisPro 1.171.43.129a (Rigaku OD, 2024)'
_computing_data_collection       'CrysAlisPro 1.171.43.129a (Rigaku OD, 2024)'
_computing_data_reduction        'CrysAlisPro 1.171.43.129a (Rigaku OD, 2024)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2019/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      100.00(17)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            'HyPix-Arc 150'
_diffrn_measured_fraction_theta_full 0.999
_diffrn_measured_fraction_theta_max 0.981
_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     40.00  84.00   0.50    0.05    --   60.32  15.00-180.00   88
  2  \w     42.00 102.00   0.50    0.05    --   60.32  15.00-120.00  120
  3  \w     64.00 119.00   0.50    0.05    --   74.97  15.00-120.00  110
  4  \w     45.00 102.00   0.50    0.05    --   60.32  15.00 -60.00  114
  5  \w     55.00 119.00   0.50    0.05    --   74.97  15.00 -30.00  128
  6  \w     55.00 119.00   0.50    0.05    --   75.09  15.00 120.00  128
  7  \w     29.00  84.00   0.50    0.05    --   60.32-125.00 -90.00  110
  8  \w     27.00  84.00   0.50    0.05    --   60.32-125.00-150.00  114
  9  \w     36.00  84.00   0.50    0.05    --   75.09-100.00 158.00   96
 10  \w     36.00  84.00   0.50    0.05    --   74.97-100.00 158.00   96
 11  \w     21.00  69.00   0.50    0.05    --   60.32-100.00 158.00   96
 12  \w   -113.00 -68.00   0.50    0.05    --  -75.57 -15.00  60.00   90
 13  \w    -88.00 -62.00   0.50    0.05    --  -60.72 -15.00  60.00   52
 14  \w   -105.00 -78.00   0.50    0.05    --  -60.72 -15.00 -30.00   54
 15  \w    -74.00 -44.00   0.50    0.05    --  -60.72 -15.00 -30.00   60
 16  \w    -70.00 -44.00   0.50    0.05    --  -60.72 -15.00-150.00   52
 17  \w    -83.00 -34.00   0.50    0.05    --  -74.06 100.00 -96.00   98
 18  \w    -74.00 -49.00   0.50    0.05    --  -60.72 125.00-180.00   50
 19  \w    -98.00 -50.00   0.50    0.05    --  -74.06 125.00-180.00   96
 20  \w    -98.00 -31.00   0.50    0.05    --  -74.06 125.00-150.00  134
 21  \w    -88.00 -31.00   0.50    0.05    --  -74.06 125.00 -30.00  114
 22  \w    -83.00 -39.00   0.50    0.05    --  -75.57 100.00 -96.00   88
 23  \w    -86.00 -31.00   0.50    0.05    --  -74.06 125.00  60.00  110
 24  \w    -94.00 -53.00   0.50    0.05    --  -75.57 125.00 120.00   82
 25  \w    -98.00 -44.00   0.50    0.05    --  -75.57 125.00 150.00  108
 26  \w    -66.00 -40.00   0.50    0.05    --  -60.72 125.00 120.00   52
 27  \w    -69.00 -21.00   0.50    0.05    --  -60.72 100.00 -96.00   96
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy R, DW system, HyPix-Arc 150'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0469202000
_diffrn_orient_matrix_UB_12      -0.0894723000
_diffrn_orient_matrix_UB_13      -0.0465190000
_diffrn_orient_matrix_UB_21      0.0813550000
_diffrn_orient_matrix_UB_22      -0.0533552000
_diffrn_orient_matrix_UB_23      0.0287935000
_diffrn_orient_matrix_UB_31      -0.0043896000
_diffrn_orient_matrix_UB_32      -0.0337932000
_diffrn_orient_matrix_UB_33      0.0776686000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Cu K\a'
_diffrn_radiation_wavelength     1.54178
_diffrn_reflns_av_R_equivalents  0.0653
_diffrn_reflns_av_unetI/netI     0.0358
_diffrn_reflns_Laue_measured_fraction_full 0.999
_diffrn_reflns_Laue_measured_fraction_max 0.981
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -22
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       15
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            42503
_diffrn_reflns_point_group_measured_fraction_full 0.999
_diffrn_reflns_point_group_measured_fraction_max 0.981
_diffrn_reflns_theta_full        67.679
_diffrn_reflns_theta_max         71.728
_diffrn_reflns_theta_min         2.695
_diffrn_source                   'Rotating-anode X-ray tube'
_diffrn_source_target            Mo
_diffrn_source_type              'Rigaku (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    15.218
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.63666
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.43.129a (Rigaku Oxford Diffraction, 2024)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            'clear light colourless'
_exptl_crystal_colour_lustre     clear
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    colourless
_exptl_crystal_density_diffrn    1.836
_exptl_crystal_density_method    'not measured'
_exptl_crystal_description       block
_exptl_crystal_F_000             2264
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.1
_refine_diff_density_max         0.940
_refine_diff_density_min         -0.909
_refine_diff_density_rms         0.128
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.085
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     517
_refine_ls_number_reflns         8127
_refine_ls_number_restraints     424
_refine_ls_restrained_S_all      1.106
_refine_ls_R_factor_all          0.0483
_refine_ls_R_factor_gt           0.0432
_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^)+(0.0260P)^2^+31.1385P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1064
_refine_ls_wR_factor_ref         0.1087
_reflns_Friedel_coverage         0.000
_reflns_number_gt                7207
_reflns_number_total             8127
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5dt00057b2.cif
_cod_data_source_block           1_CCDC2
_cod_depositor_comments
'Adding full bibliography for 7718284--7718286.cif.'
_cod_original_cell_volume        4230.69(12)
_cod_database_code               7718286
_shelx_shelxl_version_number     2019/3
_chemical_oxdiff_formula         'C H P Mn Cl'
_shelx_estimated_absorpt_t_max   0.311
_shelx_estimated_absorpt_t_min   0.242
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Mn1 \\sim Br3 \\sim Br4 \\sim Br3A \\sim Br4A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C6 \\sim C7 \\sim C8 \\sim C9 \\sim C10 \\sim P2 \\sim C6A \\sim C7A \\sim C8A
\\sim C9A \\sim C10A \\sim P2A: within 2A with sigma of 0.01 and sigma for
terminal atoms of 0.02 within 2A
Mn2 \\sim Br5 \\sim Br6 \\sim Br7 \\sim Br8 \\sim Br5A \\sim Br6A \\sim Br7A
\\sim Br8A: within 2A with sigma of 0.01 and sigma for terminal atoms of 0.02
within 2A
P1 \\sim C4 \\sim C5 \\sim C4A \\sim C5A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
C16 \\sim C17 \\sim C18 \\sim C19 \\sim C20 \\sim P4 \\sim C16A \\sim C17A
\\sim C18A \\sim C19A \\sim C20A \\sim P4A: within 2A with sigma of 0.01 and
sigma for terminal atoms of 0.02 within 2A
Uanis(C6A) \\sim Ueq, Uanis(C16A) \\sim Ueq: with sigma of 0.003 and sigma for
terminal atoms of 0.006
3. Same fragment restrains
{Mn1, Br3A, Br4A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{Mn1, Br3, Br4}
{Mn2, Br5A, Br6A, Br7A, Br8A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{Mn2, Br5, Br6, Br7, Br8}
{P1, C4A, C5A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{P1, C4, C5}
{C6A, C7A, C8A, C9A, C10A, P2A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{C6, C7, C8, C9, C10, P2}
{C16A, C17A, C18A, C19A, C20A, P4A} sigma for 1-2: 0.01, 1-3: 0.01
as in
{C16, C17, C18, C19, C20, P4}
4. Others
 Sof(Br3A)=Sof(Br4A)=1-FVAR(1)
 Sof(Br3)=Sof(Br4)=FVAR(1)
 Sof(C16A)=Sof(H16D)=Sof(H16E)=Sof(H16F)=Sof(C17A)=Sof(H17D)=Sof(H17E)=
 Sof(H17F)=Sof(C18A)=Sof(H18D)=Sof(H18E)=Sof(H18F)=Sof(C19A)=Sof(H19C)=
 Sof(H19D)=Sof(C20A)=Sof(H20D)=Sof(H20E)=Sof(H20F)=Sof(P4A)=1-FVAR(2)
 Sof(C16)=Sof(H16A)=Sof(H16B)=Sof(H16C)=Sof(C17)=Sof(H17A)=Sof(H17B)=Sof(H17C)=
 Sof(C18)=Sof(H18A)=Sof(H18B)=Sof(H18C)=Sof(C19)=Sof(H19A)=Sof(H19B)=Sof(C20)=
 Sof(H20A)=Sof(H20B)=Sof(H20C)=Sof(P4)=FVAR(2)
 Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(H5AC)=1-FVAR(3)
 Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(H5C)=FVAR(3)
 Sof(Br5A)=Sof(Br6A)=Sof(Br7A)=Sof(Br8A)=1-FVAR(4)
 Sof(Br5)=Sof(Br6)=Sof(Br7)=Sof(Br8)=FVAR(4)
 Sof(C6A)=Sof(H6AA)=Sof(H6AB)=Sof(H6AC)=Sof(C7A)=Sof(H7AA)=Sof(H7AB)=Sof(H7AC)=
 Sof(C8A)=Sof(H8AA)=Sof(H8AB)=Sof(H8AC)=Sof(C9A)=Sof(H9AA)=Sof(H9AB)=Sof(C10A)=
 Sof(H10D)=Sof(H10E)=Sof(H10F)=Sof(P2A)=1-FVAR(5)
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C7)=Sof(H7A)=Sof(H7B)=Sof(H7C)=Sof(C8)=
 Sof(H8A)=Sof(H8B)=Sof(H8C)=Sof(C9)=Sof(H9A)=Sof(H9B)=Sof(C10)=Sof(H10A)=
 Sof(H10B)=Sof(H10C)=Sof(P2)=FVAR(5)
5.a Secondary CH2 refined with riding coordinates:
 C14(H14A,H14B), C4(H4A,H4B), C9(H9A,H9B), C19(H19A,H19B), C9A(H9AA,H9AB),
 C19A(H19C,H19D), C4A(H4AA,H4AB)
5.b Idealised Me refined as rotating group:
 C1(H1A,H1B,H1C), C2(H2A,H2B,H2C), C3(H3A,H3B,H3C), C11(H11A,H11B,H11C),
 C12(H12A,H12B,H12C), C13(H13A,H13B,H13C), C15(H15A,H15B,H15C), C5(H5A,H5B,H5C),
  C6(H6A,H6B,H6C), C7(H7A,H7B,H7C), C8(H8A,H8B,H8C), C10(H10A,H10B,H10C),
 C16(H16A,H16B,H16C), C17(H17A,H17B,H17C), C18(H18A,H18B,H18C), C20(H20A,H20B,
 H20C), C6A(H6AA,H6AB,H6AC), C7A(H7AA,H7AB,H7AC), C8A(H8AA,H8AB,H8AC),
 C10A(H10D,H10E,H10F), C16A(H16D,H16E,H16F), C17A(H17D,H17E,H17F), C18A(H18D,
 H18E,H18F), C20A(H20D,H20E,H20F), C5A(H5AA,H5AB,H5AC)
;
_shelx_res_checksum              80061
_shelx_hkl_checksum              47377
_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 1.829
_oxdiff_exptl_absorpt_empirical_full_min 0.664