Aggregation-induced structural clamping drives NIR photoluminescence switching in Au2Cu6 nanoclusters by suppressing El-Sayed-allowed intersystem crossing
Yamauchi, Hayato; Arima, Daichi; Mitsui, Masaaki; Chemical Communications  (2026) –; doi:10.1039/D6CC01220E

data_7135737
_publ_section_title
;
 Aggregation-induced structural clamping drives NIR photoluminescence
 switching in Au<sub>2</sub>Cu<sub>6</sub> nanoclusters by suppressing
 El-Sayed-allowed intersystem crossing.
;
_journal_issue                   35
_journal_name_full               'Chemical communications (Cambridge, England)'
_journal_page_first              8905
_journal_page_last               8909
_journal_paper_doi               10.1039/d6cc01220e
_journal_volume                  62
_journal_year                    2026
_chemical_formula_moiety         'C51 H66 Au Cu3 P S3'
_chemical_formula_sum            'C51 H66 Au Cu3 P S3'
_chemical_formula_weight         1193.77
_chemical_name_systematic        Monoclinic
_chemical_properties_physical    Air-sensitive,Heat-sensitive
_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   geom
_atom_sites_solution_primary     dual
_audit_creation_date             2024-06-13
_audit_creation_method
;
Olex2 1.5
(compiled 2024.02.16 svn.r378c4104 for OlexSys, GUI svn.r6928)
;
_audit_update_record
;
2026-02-26 deposited with the CCDC.	2026-04-13 downloaded from the CCDC.
;
_cell_angle_alpha                66.822(10)
_cell_angle_beta                 69.544(10)
_cell_angle_gamma                84.982(10)
_cell_formula_units_Z            2
_cell_length_a                   13.674(5)
_cell_length_b                   15.457(6)
_cell_length_c                   17.319(6)
_cell_measurement_reflns_used    9599
_cell_measurement_temperature    273.15
_cell_measurement_theta_max      25.909
_cell_measurement_theta_min      2.205
_cell_volume                     3148(2)
_computing_cell_refinement       'SAINT V8.40A (Bruker, 2019)'
_computing_data_reduction        'SAINT V8.40A (Bruker, 2019)'
_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_temperature      273.15
_diffrn_measured_fraction_theta_full 0.998
_diffrn_measured_fraction_theta_max 0.993
_diffrn_measurement_device_type  'Bruker APEX-II CCD'
_diffrn_measurement_method       '\f and \w scans'
_diffrn_radiation_type           MoK\a
_diffrn_radiation_wavelength     0.71073
_diffrn_reflns_av_R_equivalents  0.1284
_diffrn_reflns_av_unetI/netI     0.0637
_diffrn_reflns_Laue_measured_fraction_full 0.998
_diffrn_reflns_Laue_measured_fraction_max 0.993
_diffrn_reflns_limit_h_max       16
_diffrn_reflns_limit_h_min       -17
_diffrn_reflns_limit_k_max       20
_diffrn_reflns_limit_k_min       -20
_diffrn_reflns_limit_l_max       22
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            143610
_diffrn_reflns_point_group_measured_fraction_full 0.998
_diffrn_reflns_point_group_measured_fraction_max 0.993
_diffrn_reflns_theta_full        25.242
_diffrn_reflns_theta_max         27.601
_diffrn_reflns_theta_min         1.702
_diffrn_source_current           1.0
_diffrn_source_power             0.05
_diffrn_source_voltage           50.0
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    3.474
_exptl_absorpt_correction_T_max  0.7456
_exptl_absorpt_correction_T_min  0.6361
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016/2) was used for absorption correction.
wR2(int) was 0.1268 before and 0.0830 after correction.
The Ratio of minimum to maximum transmission is 0.8531.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'dark red'
_exptl_crystal_colour_modifier   dark
_exptl_crystal_colour_primary    red
_exptl_crystal_density_diffrn    1.260
_exptl_crystal_description       needle
_exptl_crystal_F_000             1202
_exptl_crystal_preparation       'diffusion method,Luminescent'
_exptl_crystal_recrystallization_method
'Re-crystallisation from solvent: THF/n-Hexane'
_exptl_crystal_size_max          0.1
_exptl_crystal_size_mid          0.01
_exptl_crystal_size_min          0.01
_refine_diff_density_max         0.991
_refine_diff_density_min         -1.463
_refine_diff_density_rms         0.142
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.029
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     535
_refine_ls_number_reflns         14525
_refine_ls_number_restraints     18
_refine_ls_restrained_S_all      1.032
_refine_ls_R_factor_all          0.0662
_refine_ls_R_factor_gt           0.0410
_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^)+(0.0618P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1009
_refine_ls_wR_factor_ref         0.1153
_reflns_Friedel_coverage         0.000
_reflns_number_gt                10852
_reflns_number_total             14525
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d6cc01220e2.cif
_cod_data_source_block           240613ag29_0m
_cod_depositor_comments          'Adding full bibliography for 7135737.cif.'
_cod_original_cell_volume        3147(2)
_cod_database_code               7135737
_shelx_shelxl_version_number     2019/3
_shelx_estimated_absorpt_t_max   0.966
_shelx_estimated_absorpt_t_min   0.723
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups
2. Uiso/Uaniso restraints and constraints
Uanis(C018) \\sim Ueq, Uanis(C011) \\sim Ueq, Uanis(C01G) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
3.a Ternary CH refined with riding coordinates:
 C00Q(H00R), C00R(H00S), C00T(H00T), C011(H011), C013(H013), C01A(H01J),
 C01G(H01S), C01I(H01U), C01K(H01X)
3.b Secondary CH2 refined with riding coordinates:
 C00D(H00B,H00C), C00I(H00D,H00E), C00J(H00F,H00G), C00K(H00I,H00J), C00L(H00K,
 H00L), C00P(H00P,H00Q), C00U(H00U,H00V), C00V(H00W,H00X), C00X(H00Z,H),
 C00Y(H00,HA), C016(H01A,H01B), C017(H01C,H01D), C018(H01E,H01F), C01C(H01L,
 H01M), C01D(H01N,H01O), C01J(H01V,H01W), C01M(H01Z,HD), C01N(H01,HE)
3.c Aromatic/amide H refined with riding coordinates:
 C00A(H00A), C00H(H00H), C00M(H00M), C00N(H00N), C00O(H00O), C00W(H00Y),
 C00Z(H1), C010(H010), C012(H012), C015(H015), C01B(H01K), C01H(H01T)
3.d Idealised Me refined as rotating group:
 C019(H01G,H01H,H01I), C01E(H01P,H01Q,H01R), C01L(H01Y,HB,HC)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              18483
_shelx_hkl_checksum              67242
_shelx_fab_checksum              53573
_olex2_exptl_crystal_mounting_method
;
;
_olex2_submission_special_instructions 'No special instructions were received'