Multifunctional applications enabled by tunable multi-emission and ultra-broadband VIS-NIR luminescence <i>via</i> energy transfer in Sn<sup>2+</sup>/Mn<sup>2+</sup>-doped lead-free Zn-based metal halides.
Yang, Yongqi; Ke, Bao; Yang, Chengzhi; Xue, Yang; Huang, Kaihuang; Lu, Xintong; Zou, Bingsuo; Materials horizons 12 (2025) 2564–2576; doi:10.1039/d4mh01821d

data_1573731
_publ_section_title
;
 Multifunctional applications enabled by tunable multi-emission and
 ultra-broadband VIS-NIR luminescence <i>via</i> energy transfer in
 Sn<sup>2+</sup>/Mn<sup>2+</sup>-doped lead-free Zn-based metal halides.
;
_journal_issue                   8
_journal_name_full               'Materials horizons'
_journal_page_first              2564
_journal_page_last               2576
_journal_paper_doi               10.1039/d4mh01821d
_journal_volume                  12
_journal_year                    2025
_chemical_formula_moiety         '2(C12 H28 N), Br4 Zn'
_chemical_formula_sum            'C24 H56 Br4 N2 Zn'
_chemical_formula_weight         757.71
_space_group_crystal_system      monoclinic
_space_group_IT_number           15
_space_group_name_Hall           '-I 2ya'
_space_group_name_H-M_alt        'I 1 2/a 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2024-06-28
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2024-09-22 deposited with the CCDC.	2025-01-21 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 96.596(2)
_cell_angle_gamma                90
_cell_formula_units_Z            8
_cell_length_a                   15.0869(3)
_cell_length_b                   14.2481(2)
_cell_length_c                   31.3091(5)
_cell_measurement_reflns_used    14921
_cell_measurement_temperature    296.00
_cell_measurement_theta_max      73.4440
_cell_measurement_theta_min      3.4340
_cell_volume                     6685.6(2)
_computing_cell_refinement       'CrysAlisPro 1.171.41.49a (Rigaku OD, 2019)'
_computing_data_collection       'CrysAlisPro 1.171.41.49a (Rigaku OD, 2019)'
_computing_data_reduction        'CrysAlisPro 1.171.41.49a (Rigaku OD, 2019)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'XL  (Sheldrick, 2008)'
_computing_structure_solution    'SHELXT 2018/2 (Sheldrick, 2018)'
_diffrn_ambient_temperature      296.00
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.997
_diffrn_measured_fraction_theta_max 0.983
_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   -100.00  -5.00   0.50    0.05    --  -39.95 -77.00   0.00  190
  2  \w    -63.00  35.00   0.50    0.05    --  -39.95  57.00 150.00  196
  3  \w    -25.00  44.00   0.50    0.05    --  -39.95  19.00  60.00  138
  4  \w   -104.00 -56.00   0.50    0.05    --  -39.95-178.00-150.00   96
  5  \w    -26.00  46.00   0.50    0.05    --  -39.95  19.00 120.00  144
  6  \w     64.00 123.00   0.50    0.05    --   39.95 178.00 -60.00  118
  7  \w    -18.00  21.00   0.50    0.05    --   39.95 -19.00 -90.00   78
  8  \w    -86.00 -36.00   0.50    0.20    --  -94.50 125.00  30.00  100
  9  \w    -55.00 -26.00   0.50    0.20    --  -94.50  61.00-150.00   58
 10  \w   -177.00 -58.00   0.50    0.20    --  -94.50 -30.00 120.00  238
 11  \w    -71.00 -37.00   0.50    0.20    --  -94.50  61.00  30.00   68
 12  \w   -118.00 -83.00   0.50    0.20    --  -94.50 -94.00-120.00   70
 13  \w   -168.00-142.00   0.50    0.20    --  -94.50 -94.00-120.00   52
 14  \w    -51.00 -15.00   0.50    0.20    --  -94.50  45.00 -90.00   72
 15  \w    -56.00 -19.00   0.50    0.20    --  -94.50  61.00 120.00   74
 16  \w     34.00  59.00   0.50    0.20    --  108.87 -77.00-150.00   50
 17  \w     93.00 120.00   0.50    0.20    --  108.87   0.00-150.00   54
 18  \w     31.00  68.00   0.50    0.20    --  108.87   0.00-150.00   74
 19  \w     38.00  71.00   0.50    0.20    --  108.87 -61.00-150.00   66
 20  \w     31.00  57.00   0.50    0.20    --  108.87 -94.00   0.00   52
 21  \w     37.00  95.00   0.50    0.20    --  108.87 -77.00  90.00  116
 22  \w     29.00  61.00   0.50    0.20    --  108.87-102.00 -34.46   64
 23  \w     73.00 111.00   0.50    0.20    --  108.87-125.00   0.00   76
 24  \w     69.00 103.00   0.50    0.20    --  108.87 -94.00   0.00   68
 25  \w     39.00 106.00   0.50    0.20    --  108.87-125.00 -30.00  134
 26  \w     34.00  62.00   0.50    0.20    --  108.87 -61.00  30.00   56
 27  \w     35.00  64.00   0.50    0.20    --  108.87 -77.00-180.00   58
 28  \w     29.00  86.00   0.50    0.20    --  108.87   0.00   0.00  114
 29  \w    124.00 177.00   0.50    0.20    --  108.87   0.00-150.00  106
 30  \w     71.00 110.00   0.50    0.20    --  108.87-125.00-120.00   78
 31  \w     72.00  97.00   0.50    0.20    --  108.87 -94.00 150.00   50
 32  \w     34.00  59.00   0.50    0.20    --  108.87 -61.00 150.00   50
 33  \w     34.00  62.00   0.50    0.20    --  108.87 -94.00 150.00   56
 34  \w     81.00 106.00   0.50    0.20    --  108.87 -77.00 -30.00   50
 35  \w     35.00  62.00   0.50    0.20    --  108.87 -77.00 -30.00   54
 36  \w    120.00 165.00   0.50    0.20    --  108.87  45.00  30.00   90
 37  \w     51.00  77.00   0.50    0.20    --  108.87 -94.00 -90.00   52
 38  \w     83.00 111.00   0.50    0.20    --  108.87-125.00-180.00   56
 39  \w     80.00 111.00   0.50    0.20    --  108.87  45.00  30.00   62
 40  \w     99.00 178.00   0.50    0.20    --  108.87   0.00   0.00  158
 41  \w     77.00 103.00   0.50    0.20    --  108.87 -94.00  90.00   52
 42  \w     81.00 106.00   0.50    0.20    --  108.87 -77.00-180.00   50
 43  \w     31.00  56.00   0.50    0.20    --  108.87 -94.00  90.00   50
 44  \w     82.00 107.00   0.50    0.20    --  108.87-102.00 -34.46   50
 45  \w     86.00 111.00   0.50    0.20    --  108.87-125.00 -60.00   50
 46  \w     42.00  68.00   0.50    0.20    --  108.87-125.00   0.00   52
 47  \w     76.00  96.00   0.50    0.20    --  108.87-104.00  57.97   40
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'XtaLAB Synergy, Dualflex, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      -0.0537246000
_diffrn_orient_matrix_UB_12      -0.0285343000
_diffrn_orient_matrix_UB_13      0.0368967000
_diffrn_orient_matrix_UB_21      0.0336468000
_diffrn_orient_matrix_UB_22      -0.1016788000
_diffrn_orient_matrix_UB_23      -0.0028080000
_diffrn_orient_matrix_UB_31      0.0809301000
_diffrn_orient_matrix_UB_32      0.0232570000
_diffrn_orient_matrix_UB_33      0.0329191000
_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  0.1281
_diffrn_reflns_av_unetI/netI     0.0824
_diffrn_reflns_Laue_measured_fraction_full 0.997
_diffrn_reflns_Laue_measured_fraction_max 0.983
_diffrn_reflns_limit_h_max       18
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       17
_diffrn_reflns_limit_k_min       -17
_diffrn_reflns_limit_l_max       38
_diffrn_reflns_limit_l_min       -38
_diffrn_reflns_number            33243
_diffrn_reflns_point_group_measured_fraction_full 0.997
_diffrn_reflns_point_group_measured_fraction_max 0.983
_diffrn_reflns_theta_full        67.684
_diffrn_reflns_theta_max         74.000
_diffrn_reflns_theta_min         2.842
_diffrn_source                   'micro-focus sealed X-ray tube'
_diffrn_source_type              'PhotonJet (Cu) X-ray Source'
_exptl_absorpt_coefficient_mu    6.705
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.24162
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.41.49a (Rigaku Oxford Diffraction, 2019)
Empirical absorption correction using spherical harmonics,
 implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_density_diffrn    1.506
_exptl_crystal_description       block
_exptl_crystal_F_000             3072
_exptl_crystal_size_max          0.15
_exptl_crystal_size_mid          0.13
_exptl_crystal_size_min          0.12
_refine_diff_density_max         0.869
_refine_diff_density_min         -1.846
_refine_diff_density_rms         0.201
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.036
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     345
_refine_ls_number_reflns         6675
_refine_ls_number_restraints     194
_refine_ls_restrained_S_all      1.033
_refine_ls_R_factor_all          0.0839
_refine_ls_R_factor_gt           0.0768
_refine_ls_shift/su_max          0.002
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1568P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.2031
_refine_ls_wR_factor_ref         0.2144
_reflns_Friedel_coverage         0.000
_reflns_number_gt                5506
_reflns_number_total             6675
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d4mh01821d2.cif
_cod_data_source_block           26-1
_cod_depositor_comments          'Adding full bibliography for 1573731.cif.'
_cod_database_code               1573731
_shelx_shelxl_version_number     2019/2
_chemical_oxdiff_formula         'C N H O'
_shelx_estimated_absorpt_t_max   0.500
_shelx_estimated_absorpt_t_min   0.433
_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. Restrained distances
 C5-C4 = C5A-C4A
 1.52 with sigma of 0.01
 C2-C1 = C2A-C1A
 1.52 with sigma of 0.01
 N1-C4 \\sim N1-C4A
 with sigma of 0.02
 C6-C5 \\sim C6A-C5A
 with sigma of 0.02
 C4-C5 \\sim C4A-C5A
 with sigma of 0.02
 N1-C5 \\sim N1-C5A
 with sigma of 0.04
 C6-C4 \\sim C6A-C4A
 with sigma of 0.04
 N1-C3 \\sim N1-C3A
 with sigma of 0.02
 C1-C2 \\sim C1A-C2A
 with sigma of 0.02
 C3-C2 \\sim C3A-C2A
 with sigma of 0.02
 N1-C2 \\sim N1-C2A
 with sigma of 0.04
 C1-C3 \\sim C1A-C3A
 with sigma of 0.04
 C2A-C1A \\sim C2-C1 \\sim C3-C2 \\sim C3A-C2A \\sim C5A-C4A \\sim C5-C4 \\sim
C6-C5 \\sim C6A-C5A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
N1 \\sim C6 \\sim C1 \\sim C3 \\sim C4 \\sim C5 \\sim C2 \\sim C4A \\sim C5A
\\sim C6A \\sim C3A \\sim C2A \\sim C1A: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
4. Others
 Sof(C4A)=Sof(H4AA)=Sof(H4AB)=Sof(C5A)=Sof(H5AA)=Sof(H5AB)=Sof(C6A)=Sof(H6AA)=
 Sof(H6AB)=Sof(H6AC)=Sof(C3A)=Sof(H3AA)=Sof(H3AB)=Sof(C2A)=Sof(H2AA)=Sof(H2AB)=
 Sof(C1A)=Sof(H1AA)=Sof(H1AB)=Sof(H1AC)=1-FVAR(1)
 Sof(C6)=Sof(H6A)=Sof(H6B)=Sof(H6C)=Sof(C1)=Sof(H1A)=Sof(H1B)=Sof(H1C)=Sof(C3)=
 Sof(H3A)=Sof(H3B)=Sof(C4)=Sof(H4A)=Sof(H4B)=Sof(C5)=Sof(H5A)=Sof(H5B)=Sof(C2)=
 Sof(H2A)=Sof(H2B)=FVAR(1)
5.a Riding coordinates:
 C7(H7A,H7B,H7C)
5.b Secondary CH2 refined with riding coordinates:
 C15(H15A,H15B), C21(H21A,H21B), C9(H9A,H9B), C20(H20A,H20B), C22(H22A,H22B),
 C10(H10A,H10B), C16(H16A,H16B), C14(H14A,H14B), C17(H17A,H17B), C23(H23A,H23B),
  C8(H8A,H8B), C11(H11A,H11B), C3(H3A,H3B), C4(H4A,H4B), C5(H5A,H5B), C2(H2A,
 H2B), C4A(H4AA,H4AB), C5A(H5AA,H5AB), C3A(H3AA,H3AB), C2A(H2AA,H2AB)
5.c Idealised Me refined as rotating group:
 C13(H13A,H13B,H13C), C18(H18A,H18B,H18C), C12(H12A,H12B,H12C), C19(H19A,H19B,
 H19C), C24(H24A,H24B,H24C), C6(H6A,H6B,H6C), C1(H1A,H1B,H1C), C6A(H6AA,H6AB,
 H6AC), C1A(H1AA,H1AB,H1AC)
;
_shelx_res_checksum              19149
_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 7.607
_oxdiff_exptl_absorpt_empirical_full_min 0.239