α-Hydroxyalkynyl-protected copper(I) acetelyenediide nanoclusters with anion-dependent photoluminescence.
Yao, Jun-Fei; Zhao, Pei; Hu, Feng; Yang, Ya-Nan; Nan, Zi-Ang; Huang, Qiu-Qin; Li, Jing-Yu; Chen, Jian; Lei, Zhen; Wei, Qiao-Hua; Ehara, Masahiro; Wang, Quan-Ming; Nanoscale 17 (2025) 25289–25296; doi:10.1039/d5nr03301b

data_1576092
_publ_section_title
;
 &#x3b1;-Hydroxyalkynyl-protected copper(I) acetelyenediide nanoclusters
 with anion-dependent photoluminescence.
;
_journal_issue                   43
_journal_name_full               Nanoscale
_journal_page_first              25289
_journal_page_last               25296
_journal_paper_doi               10.1039/d5nr03301b
_journal_volume                  17
_journal_year                    2025
_chemical_formula_moiety         'C205 H242 Cl Cu15 O27, 2(Cl O4)'
_chemical_formula_sum            'C205 H242 Cl3 Cu15 O35'
_chemical_formula_weight         4325.42
_space_group_crystal_system      monoclinic
_space_group_IT_number           4
_space_group_name_Hall           'P 2yb'
_space_group_name_H-M_alt        'P 1 21 1'
_atom_sites_solution_hydrogens   mixed
_atom_sites_solution_primary     dual
_audit_creation_date             2025-03-07
_audit_creation_method
;
Olex2 1.5
(compiled 2025.03.04 svn.red2d20d0 for OlexSys, GUI svn.r7181)
;
_audit_update_record
;
2025-03-08 deposited with the CCDC.	2025-10-23 downloaded from the CCDC.
;
_cell_angle_alpha                90
_cell_angle_beta                 92.990(2)
_cell_angle_gamma                90
_cell_formula_units_Z            2
_cell_length_a                   16.3979(3)
_cell_length_b                   23.0681(5)
_cell_length_c                   31.5330(5)
_cell_measurement_reflns_used    32780
_cell_measurement_temperature    200.00(10)
_cell_measurement_theta_max      55.7460
_cell_measurement_theta_min      2.0770
_cell_volume                     11911.7(4)
_computing_cell_refinement       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_collection       'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_data_reduction        'CrysAlisPro 1.171.42.49 (Rigaku OD, 2022)'
_computing_molecular_graphics    'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 1.5 (Dolomanov et al., 2009)'
_computing_structure_refinement  'SHELXL 2018/3 (Sheldrick, 2015)'
_computing_structure_solution    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_environment      N~2~
_diffrn_ambient_temperature      200.00(10)
_diffrn_detector                 'Hybrid Pixel Array Detector'
_diffrn_detector_area_resol_mean 10.0000
_diffrn_detector_type            HyPix
_diffrn_measured_fraction_theta_full 0.950
_diffrn_measured_fraction_theta_max 0.950
_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   -115.00 -45.00   0.50    1.10    --  -69.39 139.00 111.00  140
  2  \w   -115.00 -26.00   0.50    1.10    --  -69.39 130.00 -63.00  178
  3  \w    -83.00 -38.00   0.50    1.10    --  -69.39  57.00 -60.00   90
  4  \w    -20.00   5.00   0.50    1.10    --  -69.39  57.00 -60.00   50
  5  \w     14.00  74.00   0.50    0.30    --   -0.62  57.00-120.00  120
  6  \w   -135.00-105.00   0.50    1.10    --  -69.39 -99.00 -30.00   60
  7  \w   -107.00 -70.00   0.50    1.10    --  -69.39-139.00  51.00   74
  8  \w   -140.00 -79.00   0.50    1.10    --  -69.39-125.00  90.00  122
  9  \w   -139.00 -88.00   0.50    1.10    --  -69.39 -99.00-120.00  102
 10  \w   -109.00 -84.00   0.50    1.10    --  -69.39-130.00-134.00   50
 11  \w    -71.00 -36.00   0.50    0.30    --   -0.62 -57.00-180.00   70
 12  \w      6.00  32.00   0.50    0.30    --   -0.62 -99.00 -60.00   52
 13  \w     62.00  88.00   0.50    1.10    --   68.14-125.00 -30.00   52
 14  \w      9.00  37.00   0.50    0.30    --   -0.62 -99.00 120.00   56
 15  \w     -6.00  91.00   0.50    1.10    --   68.14 -57.00-150.00  194
 16  \w     -5.00  71.00   0.50    1.10    --   68.14 -38.00-120.00  152
 17  \w     84.00 109.00   0.50    1.10    --   68.14 130.00 -63.00   50
 18  \w     81.00 106.00   0.50    1.10    --   68.14 139.00 111.00   50
;
_diffrn_measurement_device       'four-circle diffractometer'
_diffrn_measurement_device_type  'ROD, Synergy Custom system, HyPix'
_diffrn_measurement_method       '\w scans'
_diffrn_orient_matrix_type
'CrysAlisPro convention (1999,Acta A55,543-557)'
_diffrn_orient_matrix_UB_11      0.0051167000
_diffrn_orient_matrix_UB_12      0.0087245000
_diffrn_orient_matrix_UB_13      0.0420744000
_diffrn_orient_matrix_UB_21      0.0018867000
_diffrn_orient_matrix_UB_22      0.0573558000
_diffrn_orient_matrix_UB_23      -0.0063713000
_diffrn_orient_matrix_UB_31      -0.0815728000
_diffrn_orient_matrix_UB_32      0.0017897000
_diffrn_orient_matrix_UB_33      0.0002525000
_diffrn_radiation_monochromator  mirror
_diffrn_radiation_probe          x-ray
_diffrn_radiation_type           'Ga K\a'
_diffrn_radiation_wavelength     1.3405
_diffrn_reflns_av_R_equivalents  0.0927
_diffrn_reflns_av_unetI/netI     0.1087
_diffrn_reflns_Laue_measured_fraction_full 0.950
_diffrn_reflns_Laue_measured_fraction_max 0.950
_diffrn_reflns_limit_h_max       10
_diffrn_reflns_limit_h_min       -19
_diffrn_reflns_limit_k_max       26
_diffrn_reflns_limit_k_min       -26
_diffrn_reflns_limit_l_max       36
_diffrn_reflns_limit_l_min       -36
_diffrn_reflns_number            59823
_diffrn_reflns_point_group_measured_fraction_full 0.759
_diffrn_reflns_point_group_measured_fraction_max 0.759
_diffrn_reflns_theta_full        51.498
_diffrn_reflns_theta_max         51.498
_diffrn_reflns_theta_min         2.440
_diffrn_source                   'micro-focus metaljet'
_exptl_absorpt_coefficient_mu    7.589
_exptl_absorpt_correction_T_max  1.00000
_exptl_absorpt_correction_T_min  0.31791
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
CrysAlisPro 1.171.42.49 (Rigaku Oxford Diffraction, 2022)
Empirical absorption correction using spherical harmonics,
implemented in SCALE3 ABSPACK scaling algorithm.
;
_exptl_crystal_colour            yellow
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.206
_exptl_crystal_description       block
_exptl_crystal_F_000             4476
_exptl_crystal_size_max          0.25
_exptl_crystal_size_mid          0.21
_exptl_crystal_size_min          0.1
_refine_diff_density_max         2.051
_refine_diff_density_min         -1.187
_refine_diff_density_rms         0.176
_refine_ls_abs_structure_details
;
 Classical Flack method preferred over Parsons because s.u. lower.
;
_refine_ls_abs_structure_Flack   0.238(6)
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.212
_refine_ls_hydrogen_treatment    mixed
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2345
_refine_ls_number_reflns         30134
_refine_ls_number_restraints     1500
_refine_ls_restrained_S_all      1.188
_refine_ls_R_factor_all          0.1274
_refine_ls_R_factor_gt           0.1088
_refine_ls_shift/su_max          0.036
_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          0.2915
_refine_ls_wR_factor_ref         0.3082
_reflns_Friedel_coverage         0.555
_reflns_Friedel_fraction_full    0.558
_reflns_Friedel_fraction_max     0.558
_reflns_number_gt                23796
_reflns_number_total             30134
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5nr03301b2.cif
_cod_data_source_block           Cu15
_cod_depositor_comments
'Adding full bibliography for 1576092--1576093.cif.'
_cod_database_code               1576092
_shelx_shelxl_version_number     2018/3
_chemical_oxdiff_formula         'C11 H10 N O'
_shelx_estimated_absorpt_t_max   0.517
_shelx_estimated_absorpt_t_min   0.253
_diffrn_oxdiff_ac3_digest_hkl    419906eb81d3b999854f42c0a72b4467c9561a
_olex2_refinement_description
;
1. Fixed Uiso
 At 1.2 times of:
  All C(H) groups, H3 of O34, All C(H,H) groups
 At 1.5 times of:
  All C(H,H,H) groups, H122 of O122, H422 of O422, H204 of O204, H404 of O404,
   H104 of O104, H504 of O504, H1 of O1, H2 of O2, H304 of O304, H322 of O322,
  H222 of O222, H604 of O604, H944 of O944, H904 of O904, H522 of O522, H926 of
  O926, H622 of O622, H804 of O804, H722 of O722, H822 of O822, H922 of O922,
  H704 of O704
2. Restrained distances
 H3-O3
 0.84 with sigma of 0.001
 Cu15-H3
 2.4 with sigma of 0.02
 O1-H1
 0.87 with sigma of 0.01
 O2-H2
 0.87 with sigma of 0.01
 O204-H204
 0.87 with sigma of 0.01
 O304-H304
 0.87 with sigma of 0.01
 O704-H704
 0.87 with sigma of 0.01
 C3-H1
 1.88063 with sigma of 0.02
 Cu11-H1
 2.583373 with sigma of 0.02
 C4-H2
 1.863491 with sigma of 0.02
 Cu14-H2
 2.725199 with sigma of 0.02
 C203-H204
 1.922186 with sigma of 0.02
 Cu11-H204
 2.802499 with sigma of 0.02
 C303-H304
 1.917379 with sigma of 0.02
 Cu12-H304
 2.699078 with sigma of 0.02
 C703-H704
 1.931909 with sigma of 0.02
 Cu13-H704
 2.692693 with sigma of 0.02
 Cl3-O34 \\sim Cl3-O33 \\sim Cl3-O31 \\sim Cl3-O32
 with sigma of 0.001
 O31-O32 \\sim O31-O33 \\sim O31-O34 \\sim O32-O33 \\sim O32-O34 \\sim O33-O34
 with sigma of 0.001
 O1-C3 \\sim O2-C4 \\sim O3-C5
 with sigma of 0.001
3. Uiso/Uaniso restraints and constraints
O926 \\sim O944 \\sim C923 \\sim C924 \\sim C925 \\sim C927 \\sim C928 \\sim
C929 \\sim C930 \\sim C931 \\sim C932 \\sim C933 \\sim C934 \\sim C935 \\sim
C936 \\sim C937 \\sim C938 \\sim C939 \\sim C940 \\sim C941 \\sim C942 \\sim
C943: within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002
within 2A
Cl3 \\sim O31 \\sim O32 \\sim O33 \\sim O34: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
C401 \\sim C402 \\sim C403 \\sim O404: within 2A with sigma of 0.01 and sigma
for terminal atoms of 0.02 within 2A
O604 \\sim O622 \\sim C601 \\sim C602 \\sim C603 \\sim C605 \\sim C606 \\sim
C607 \\sim C608 \\sim C609 \\sim C610 \\sim C611 \\sim C612 \\sim C613 \\sim
C614 \\sim C615 \\sim C616 \\sim C617 \\sim C618 \\sim C619 \\sim C620 \\sim
C621: within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002
within 2A
Cu15 \\sim O3 \\sim C5: within 2A with sigma of 0.001 and sigma for terminal
atoms of 0.002 within 2A
O904 \\sim O922 \\sim C901 \\sim C902 \\sim C903 \\sim C905 \\sim C906 \\sim
C907 \\sim C908 \\sim C909 \\sim C910 \\sim C911 \\sim C912 \\sim C913 \\sim
C914 \\sim C915 \\sim C916 \\sim C917 \\sim C918 \\sim C919 \\sim C920 \\sim
C921: within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002
within 2A
O104 \\sim O122 \\sim C101 \\sim C102 \\sim C103 \\sim C105 \\sim C106 \\sim
C107 \\sim C108 \\sim C109 \\sim C110 \\sim C111 \\sim C112 \\sim C113 \\sim
C114 \\sim C115 \\sim C116 \\sim C117 \\sim C118 \\sim C119 \\sim C120 \\sim
C121: within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002
within 2A
O722 \\sim C701 \\sim C702 \\sim C703 \\sim C705 \\sim C706 \\sim C707 \\sim
C708 \\sim C709 \\sim C710 \\sim C711 \\sim C712 \\sim C713 \\sim C714 \\sim
C715 \\sim C716 \\sim C717 \\sim C718 \\sim C719 \\sim C720 \\sim C721: within
2A with sigma of 0.001 and sigma for terminal atoms of 0.002 within 2A
O204 \\sim O222 \\sim C201 \\sim C202 \\sim C203 \\sim C205 \\sim C206 \\sim
C207 \\sim C208 \\sim C209 \\sim C210 \\sim C211 \\sim C212 \\sim C213 \\sim
C214 \\sim C215 \\sim C216 \\sim C217 \\sim C218 \\sim C219 \\sim C220 \\sim
C221: within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002
within 2A
O804 \\sim O822 \\sim C801 \\sim C802 \\sim C803 \\sim C805 \\sim C806 \\sim
C807 \\sim C808 \\sim C809 \\sim C810 \\sim C811 \\sim C812 \\sim C813 \\sim
C814 \\sim C815 \\sim C816 \\sim C817 \\sim C818 \\sim C819 \\sim C820 \\sim
C821: within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002
within 2A
Cl1 \\sim O11 \\sim O12 \\sim O13 \\sim O14: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
Cl2 \\sim O21 \\sim O22 \\sim O23 \\sim O24: within 2A with sigma of 0.001 and
sigma for terminal atoms of 0.002 within 2A
O504 \\sim O522 \\sim C501 \\sim C502 \\sim C503 \\sim C505 \\sim C506 \\sim
C507 \\sim C508 \\sim C509 \\sim C510 \\sim C511 \\sim C512 \\sim C513 \\sim
C514 \\sim C515 \\sim C516 \\sim C517 \\sim C518 \\sim C519 \\sim C520 \\sim
C521: within 2A with sigma of 0.001 and sigma for terminal atoms of 0.002
within 2A
C1 \\sim C2: within 2A with sigma of 0.001 and sigma for terminal atoms of
0.002 within 2A
C419 \\sim C418 \\sim C417 \\sim C416 \\sim C421 \\sim C420: within 2A with
sigma of 0.01 and sigma for terminal atoms of 0.02 within 2A
C305 \\sim C306 \\sim C307 \\sim C313 \\sim C312 \\sim C311 \\sim C310 \\sim
C308 \\sim C303: within 2A with sigma of 0.01 and sigma for terminal atoms of
0.02 within 2A
C412 \\sim C417 \\sim C418 \\sim C419 \\sim C420 \\sim C421 \\sim C416 \\sim
C415 \\sim C413 \\sim C414 \\sim C407 \\sim C408: within 2A with sigma of 0.01
and sigma for terminal atoms of 0.02 within 2A
Uanis(C401) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
Uanis(C301) \\sim Ueq, Uanis(C302) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C417) \\sim Ueq: with sigma of 0.01 and sigma for terminal atoms of 0.02
4.a Ternary CH refined with riding coordinates:
 C107(H107), C112(H112), C113(H113), C207(H207), C212(H212), C213(H213),
 C307(H307), C312(H312), C313(H313), C407(H407), C412(H412), C413(H413),
 C507(H507), C512(H512), C513(H513), C607(H607), C612(H612), C613(H613),
 C707(H707), C712(H712), C713(H713), C807(H807), C812(H812), C813(H813),
 C907(H907), C912(H912), C913(H913), C929(H929), C934(H934), C935(H935)
4.b Secondary CH2 refined with riding coordinates:
 C105(H10A,H10B), C106(H10C,H10D), C110(H11A,H11B), C111(H11C,H11D), C114(H11E,
 H11F), C115(H11G,H11H), C205(H20A,H20B), C206(H20C,H20D), C210(H21A,H21B),
 C211(H21C,H21D), C214(H21E,H21F), C215(H21G,H21H), C305(H30A,H30B), C306(H30C,
 H30D), C310(H31A,H31B), C311(H31C,H31D), C314(H31E,H31F), C315(H31G,H31H),
 C405(H40A,H40B), C406(H40C,H40D), C410(H41A,H41B), C411(H41C,H41D), C414(H41E,
 H41F), C415(H41G,H41H), C505(H50A,H50B), C506(H50C,H50D), C510(H51A,H51B),
 C511(H51C,H51D), C514(H51E,H51F), C515(H51G,H51H), C605(H60A,H60B), C606(H60C,
 H60D), C610(H61A,H61B), C611(H61C,H61D), C614(H61E,H61F), C615(H61G,H61H),
 C705(H70A,H70B), C706(H70C,H70D), C710(H71A,H71B), C711(H71C,H71D), C714(H71E,
 H71F), C715(H71G,H71H), C805(H80A,H80B), C806(H80C,H80D), C810(H81A,H81B),
 C811(H81C,H81D), C814(H81E,H81F), C815(H81G,H81H), C905(H90A,H90B), C906(H90C,
 H90D), C910(H91A,H91B), C911(H91C,H91D), C914(H91E,H91F), C915(H91G,H91H),
 C927(H92A,H92B), C928(H92C,H92D), C932(H93D,H93E), C933(H93F,H93G), C936(H93H,
 H93I), C937(H93J,H93K)
4.c Aromatic/amide H refined with riding coordinates:
 C118(H118), C119(H119), C121(H121), C218(H218), C219(H219), C221(H221),
 C318(H318), C319(H319), C321(H321), C418(H418), C419(H419), C421(H421),
 C518(H518), C519(H519), C521(H521), C618(H618), C619(H619), C621(H621),
 C718(H718), C719(H719), C721(H721), C818(H818), C819(H819), C821(H821),
 C918(H918), C919(H919), C921(H921), C943(H943), C940(H940), C941(H941)
4.d Fitted hexagon refined as free rotating group:
 C616(C617,C618,C619,C620,C621), C942(C943,C938,C939,C940,C941)
4.e Tetrahedral OH refined with riding coordinates:
 O804(H804), O904(H904)
4.f Idealised Me refined as rotating group:
 C3(H3A,H3B,H3C), C4(H4A,H4B,H4C), C5(H5A,H5B,H5C), C109(H10E,H10F,H10G),
 C209(H20E,H20F,H20G), C309(H30E,H30F,H30G), C409(H40E,H40F,H40G), C509(H50E,
 H50F,H50G), C609(H60E,H60F,H60G), C709(H70E,H70F,H70G), C809(H80E,H80F,H80G),
 C909(H90E,H90F,H90G), C931(H93A,H93B,H93C)
4.g Idealised tetrahedral OH refined as rotating group:
 O104(H104), O122(H122), O222(H222), O322(H322), O404(H404), O422(H422),
 O504(H504), O522(H522), O604(H604), O622(H622), O722(H722), O822(H822),
 O922(H922), O926(H926), O944(H944)
;
_smtbx_masks_void_probe_radius   1.2
_smtbx_masks_void_truncation_radius 1.2
_shelx_res_checksum              24410
_shelx_fab_checksum              95478
_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 2.441
_oxdiff_exptl_absorpt_empirical_full_min 0.561