Icosahedron kernel defect in Pt1Agx series of bimetallic nanoclusters enhances photocatalytic hydrogen evolution
Tan, Dong; Ding, Tengfei; Shen, Kaidong; Xu, Chang; Jin, Shan; Hu, Daqiao; Sun, Song; Zhu, Manzhou; Chemical Science 16 (2025) 9326–9336; doi:10.1039/D5SC01735A

data_1574521
_publ_section_title
;
 Icosahedron kernel defect in Pt1Agx series of bimetallic nanoclusters
 enhances photocatalytic hydrogen evolution
;
_journal_issue                   21
_journal_name_full               'Chemical Science'
_journal_page_first              9326
_journal_page_last               9336
_journal_paper_doi               10.1039/D5SC01735A
_journal_volume                  16
_journal_year                    2025
_chemical_formula_moiety
'2(C177 H152 Ag11 F20 O21 P7 Pt S5), 4(C H2 Cl2)'
_chemical_formula_sum            'C358 H312 Ag22 Cl8 F40 O42 P14 Pt2 S10'
_chemical_formula_weight         9847.16
_chemical_name_systematic        Pt1Ag11(C6HF4S)5(C21H21O3P)7
_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     iterative
_audit_creation_date             2024-04-28
_audit_creation_method
;
Olex2 1.2
(compiled 2018.05.29 svn.r3508 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2024-08-30 deposited with the CCDC.	2025-04-22 downloaded from the CCDC.
;
_cell_angle_alpha                79.311(12)
_cell_angle_beta                 78.555(12)
_cell_angle_gamma                63.042(11)
_cell_formula_units_Z            2
_cell_length_a                   19.063(3)
_cell_length_b                   19.742(3)
_cell_length_c                   27.214(4)
_cell_measurement_temperature    293(2)
_cell_volume                     8894(3)
_computing_molecular_graphics    'Olex2 (Dolomanov et al., 2009)'
_computing_publication_material  'Olex2 (Dolomanov et al., 2009)'
_computing_structure_refinement  'ShelXL (Sheldrick, 2015)'
_computing_structure_solution    'olex2.solve (Bourhis et al., 2015)'
_diffrn_ambient_temperature      293(2)
_diffrn_measured_fraction_theta_full 0.964
_diffrn_measured_fraction_theta_max 0.936
_diffrn_radiation_type           CuK\a
_diffrn_radiation_wavelength     1.54186
_diffrn_reflns_av_R_equivalents  0.0571
_diffrn_reflns_av_unetI/netI     0.0651
_diffrn_reflns_Laue_measured_fraction_full 0.964
_diffrn_reflns_Laue_measured_fraction_max 0.936
_diffrn_reflns_limit_h_max       22
_diffrn_reflns_limit_h_min       -11
_diffrn_reflns_limit_k_max       23
_diffrn_reflns_limit_k_min       -18
_diffrn_reflns_limit_l_max       31
_diffrn_reflns_limit_l_min       -32
_diffrn_reflns_number            69196
_diffrn_reflns_point_group_measured_fraction_full 0.964
_diffrn_reflns_point_group_measured_fraction_max 0.936
_diffrn_reflns_theta_full        67.686
_diffrn_reflns_theta_max         70.018
_diffrn_reflns_theta_min         4.741
_exptl_absorpt_coefficient_mu    13.337
_exptl_crystal_colour            red
_exptl_crystal_density_diffrn    1.839
_exptl_crystal_F_000             4852
_refine_diff_density_max         1.732
_refine_diff_density_min         -3.070
_refine_diff_density_rms         0.191
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.033
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     2194
_refine_ls_number_reflns         31583
_refine_ls_number_restraints     2519
_refine_ls_restrained_S_all      1.065
_refine_ls_R_factor_all          0.0919
_refine_ls_R_factor_gt           0.0695
_refine_ls_shift/su_max          0.009
_refine_ls_shift/su_mean         0.000
_refine_ls_structure_factor_coef Fsqd
_refine_ls_weighting_details
'w=1/[\s^2^(Fo^2^)+(0.1391P)^2^] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1888
_refine_ls_wR_factor_ref         0.2059
_reflns_Friedel_coverage         0.000
_reflns_number_gt                22807
_reflns_number_total             31583
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            d5sc01735a2.cif
_cod_data_source_block           ap-0428_sq
_cod_depositor_comments          'Adding full bibliography for 1574521.cif.'
_cod_original_cell_volume        8894(2)
_cod_database_code               1574521
_shelx_shelxl_version_number     2018/3
_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. Restrained distances
 C11-O0AA
 1.382 with sigma of 0.01
 C31-O0AA
 1.32 with sigma of 0.01
 C11-C31
 2.34 with sigma of 0.01
 O04P-C04N
 1.44 with sigma of 0.01
 O02G-C3
 1.44 with sigma of 0.01
 C06H-O06D
 2.32 with sigma of 0.01
 O06D-C05U
 2.42 with sigma of 0.01
 H7A-H05X
 2.1 with sigma of 0.01
 H05Q-H05Z
 2.1 with sigma of 0.01
 C60-C05A
 2.42 with sigma of 0.01
 H06H-H05L
 2.1 with sigma of 0.01
 H31B_$1-H05X_$2
 2.1 with sigma of 0.01
3. Restrained planarity
 C04U, C067, C069, C11, C52, C59, O0AA, C31
 with sigma of 0.1
4. Uiso/Uaniso restraints and constraints
P00N \\sim C04U \\sim C067 \\sim C59 \\sim C52 \\sim C069 \\sim C11 \\sim O0AA
\\sim C31: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C04U \\sim C069 \\sim C067 \\sim C52 \\sim C59 \\sim C11 \\sim O0AA \\sim C31:
within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C02J \\sim C03I \\sim C05M \\sim F011 \\sim C05P \\sim C04R \\sim C02R \\sim
F00V \\sim F01A \\sim F038: within 3.8A with sigma of 0.01 and sigma for
terminal atoms of 0.02
C04U \\sim O019 \\sim C067 \\sim C59 \\sim C11 \\sim C52 \\sim C069 \\sim O0AA
\\sim C31: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C032 \\sim C05B \\sim C05U \\sim C60 \\sim C06H \\sim C05C \\sim O06D \\sim
C05A: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
P00N \\sim C04U \\sim C067 \\sim C59 \\sim C11 \\sim C52 \\sim C069 \\sim O0AA
\\sim C31: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
C032 \\sim P00N \\sim C04S \\sim C06A \\sim C06J \\sim C06E \\sim C05D \\sim
C02L \\sim O04P \\sim C04N \\sim C05B \\sim C05U \\sim C60 \\sim C06H \\sim
O06D \\sim C05A \\sim C04U \\sim C05C \\sim C067 \\sim C069 \\sim C59 \\sim C52
\\sim C11 \\sim O0AA \\sim C31: within 3.8A with sigma of 0.01 and sigma for
terminal atoms of 0.02
C3 \\sim O02G \\sim C04A \\sim C02X \\sim C040 \\sim C036 \\sim C034 \\sim P00I
\\sim C02Z: within 3.8A with sigma of 0.01 and sigma for terminal atoms of 0.02
F013 \\sim C04O \\sim S00G \\sim C043 \\sim C03J \\sim C02M \\sim C03K \\sim
C05J \\sim F02N \\sim F018: within 3.8A with sigma of 0.005 and sigma for
terminal atoms of 0.01
P00N \\sim C032 \\sim C05B \\sim C05U \\sim C60 \\sim C05A \\sim C06H \\sim
C05C \\sim O06D \\sim C04S \\sim C02L \\sim C05D \\sim C06A \\sim C06J \\sim
C06E \\sim O04P \\sim C04N \\sim C067 \\sim C04U \\sim C069 \\sim C52 \\sim C11
\\sim C59 \\sim C31 \\sim O0AA: within 3.8A with sigma of 0.005 and sigma for
terminal atoms of 0.01
Uanis(O017) \\sim Ueq, Uanis(O019) \\sim Ueq, Uanis(O01B) \\sim Ueq,
Uanis(O01C) \\sim Ueq, Uanis(O01E) \\sim Ueq, Uanis(O01I) \\sim Ueq,
Uanis(O01N) \\sim Ueq, Uanis(O01S) \\sim Ueq, Uanis(O01Z) \\sim Ueq,
Uanis(O029) \\sim Ueq, Uanis(O02G) \\sim Ueq, Uanis(O02Q) \\sim Ueq,
Uanis(O02Y) \\sim Ueq, Uanis(O04I) \\sim Ueq, Uanis(O04J) \\sim Ueq,
Uanis(O04P) \\sim Ueq, Uanis(O04V) \\sim Ueq, Uanis(O058) \\sim Ueq,
Uanis(O06D) \\sim Ueq, Uanis(O0AA) \\sim Ueq, Uanis(O2) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(F00Q) \\sim Ueq, Uanis(F00R) \\sim Ueq, Uanis(F00S) \\sim Ueq,
Uanis(F00V) \\sim Ueq, Uanis(F00W) \\sim Ueq, Uanis(F00X) \\sim Ueq,
Uanis(F00Y) \\sim Ueq, Uanis(F00Z) \\sim Ueq, Uanis(F010) \\sim Ueq,
Uanis(F011) \\sim Ueq, Uanis(F013) \\sim Ueq, Uanis(F015) \\sim Ueq,
Uanis(F018) \\sim Ueq, Uanis(F01A) \\sim Ueq, Uanis(F01D) \\sim Ueq,
Uanis(F01H) \\sim Ueq, Uanis(F01J) \\sim Ueq, Uanis(F01O) \\sim Ueq,
Uanis(F02N) \\sim Ueq, Uanis(F038) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C014) \\sim Ueq, Uanis(C016) \\sim Ueq, Uanis(C01F) \\sim Ueq,
Uanis(C01G) \\sim Ueq, Uanis(C01K) \\sim Ueq, Uanis(C01L) \\sim Ueq,
Uanis(C01M) \\sim Ueq, Uanis(C01P) \\sim Ueq, Uanis(C01Q) \\sim Ueq,
Uanis(C01R) \\sim Ueq, Uanis(C01T) \\sim Ueq, Uanis(C01U) \\sim Ueq,
Uanis(C01V) \\sim Ueq, Uanis(C01W) \\sim Ueq, Uanis(C01X) \\sim Ueq,
Uanis(C01Y) \\sim Ueq, Uanis(C020) \\sim Ueq, Uanis(C021) \\sim Ueq,
Uanis(C022) \\sim Ueq, Uanis(C023) \\sim Ueq, Uanis(C024) \\sim Ueq,
Uanis(C025) \\sim Ueq, Uanis(C026) \\sim Ueq, Uanis(C027) \\sim Ueq,
Uanis(C028) \\sim Ueq, Uanis(C02A) \\sim Ueq, Uanis(C02B) \\sim Ueq,
Uanis(C02C) \\sim Ueq, Uanis(C02D) \\sim Ueq, Uanis(C02E) \\sim Ueq,
Uanis(C02F) \\sim Ueq, Uanis(C02H) \\sim Ueq, Uanis(C02I) \\sim Ueq,
Uanis(C02J) \\sim Ueq, Uanis(C02K) \\sim Ueq, Uanis(C02L) \\sim Ueq,
Uanis(C02M) \\sim Ueq, Uanis(C02O) \\sim Ueq, Uanis(C02P) \\sim Ueq,
Uanis(C02R) \\sim Ueq, Uanis(C02S) \\sim Ueq, Uanis(C02T) \\sim Ueq,
Uanis(C02U) \\sim Ueq, Uanis(C02V) \\sim Ueq, Uanis(C02W) \\sim Ueq,
Uanis(C046) \\sim Ueq, Uanis(C04E) \\sim Ueq, Uanis(C17) \\sim Ueq, Uanis(C2AA)
\\sim Ueq, Uanis(C05Y) \\sim Ueq, Uanis(C02X) \\sim Ueq, Uanis(C02Z) \\sim Ueq,
Uanis(C030) \\sim Ueq, Uanis(C031) \\sim Ueq, Uanis(C032) \\sim Ueq,
Uanis(C033) \\sim Ueq, Uanis(C034) \\sim Ueq, Uanis(C035) \\sim Ueq,
Uanis(C036) \\sim Ueq, Uanis(C037) \\sim Ueq, Uanis(C039) \\sim Ueq,
Uanis(C03A) \\sim Ueq, Uanis(C03B) \\sim Ueq, Uanis(C03C) \\sim Ueq,
Uanis(C03D) \\sim Ueq, Uanis(C03E) \\sim Ueq, Uanis(C03F) \\sim Ueq,
Uanis(C03G) \\sim Ueq, Uanis(C03H) \\sim Ueq, Uanis(C03I) \\sim Ueq,
Uanis(C03J) \\sim Ueq, Uanis(C03K) \\sim Ueq, Uanis(C03L) \\sim Ueq,
Uanis(C03M) \\sim Ueq, Uanis(C03N) \\sim Ueq, Uanis(C03O) \\sim Ueq,
Uanis(C03P) \\sim Ueq, Uanis(C03Q) \\sim Ueq, Uanis(C03R) \\sim Ueq,
Uanis(C03S) \\sim Ueq, Uanis(C03T) \\sim Ueq, Uanis(C03U) \\sim Ueq,
Uanis(C03V) \\sim Ueq, Uanis(C03W) \\sim Ueq, Uanis(C03X) \\sim Ueq,
Uanis(C03Y) \\sim Ueq, Uanis(C03Z) \\sim Ueq, Uanis(C040) \\sim Ueq,
Uanis(C041) \\sim Ueq, Uanis(C042) \\sim Ueq, Uanis(C043) \\sim Ueq,
Uanis(C044) \\sim Ueq, Uanis(C045) \\sim Ueq, Uanis(C047) \\sim Ueq,
Uanis(C048) \\sim Ueq, Uanis(C049) \\sim Ueq, Uanis(C04A) \\sim Ueq,
Uanis(C04B) \\sim Ueq, Uanis(C04C) \\sim Ueq, Uanis(C04D) \\sim Ueq,
Uanis(C04F) \\sim Ueq, Uanis(C04H) \\sim Ueq, Uanis(C04K) \\sim Ueq,
Uanis(C04L) \\sim Ueq, Uanis(C04N) \\sim Ueq, Uanis(C04O) \\sim Ueq,
Uanis(C04Q) \\sim Ueq, Uanis(C04R) \\sim Ueq, Uanis(C04S) \\sim Ueq,
Uanis(C04T) \\sim Ueq, Uanis(C04U) \\sim Ueq, Uanis(C04W) \\sim Ueq,
Uanis(C04X) \\sim Ueq, Uanis(C05N) \\sim Ueq, Uanis(C15) \\sim Ueq, Uanis(C064)
\\sim Ueq, Uanis(C065) \\sim Ueq, Uanis(C04M) \\sim Ueq, Uanis(C04Y) \\sim Ueq,
Uanis(C04Z) \\sim Ueq, Uanis(C050) \\sim Ueq, Uanis(C051) \\sim Ueq,
Uanis(C052) \\sim Ueq, Uanis(C053) \\sim Ueq, Uanis(C054) \\sim Ueq,
Uanis(C055) \\sim Ueq, Uanis(C057) \\sim Ueq, Uanis(C059) \\sim Ueq,
Uanis(C05A) \\sim Ueq, Uanis(C05B) \\sim Ueq, Uanis(C05C) \\sim Ueq,
Uanis(C05D) \\sim Ueq, Uanis(C05E) \\sim Ueq, Uanis(C05F) \\sim Ueq,
Uanis(C05G) \\sim Ueq, Uanis(C05H) \\sim Ueq, Uanis(C05I) \\sim Ueq,
Uanis(C05J) \\sim Ueq, Uanis(C05K) \\sim Ueq, Uanis(C05L) \\sim Ueq,
Uanis(C05M) \\sim Ueq, Uanis(C05O) \\sim Ueq, Uanis(C05P) \\sim Ueq,
Uanis(C05Q) \\sim Ueq, Uanis(C05R) \\sim Ueq, Uanis(C05S) \\sim Ueq,
Uanis(C05T) \\sim Ueq, Uanis(C05U) \\sim Ueq, Uanis(C05V) \\sim Ueq,
Uanis(C05W) \\sim Ueq, Uanis(C05X) \\sim Ueq, Uanis(C05Z) \\sim Ueq,
Uanis(C060) \\sim Ueq, Uanis(C061) \\sim Ueq, Uanis(C062) \\sim Ueq,
Uanis(C063) \\sim Ueq, Uanis(C066) \\sim Ueq, Uanis(C067) \\sim Ueq,
Uanis(C068) \\sim Ueq, Uanis(C069) \\sim Ueq, Uanis(C06A) \\sim Ueq,
Uanis(C06B) \\sim Ueq, Uanis(C06C) \\sim Ueq, Uanis(C06E) \\sim Ueq,
Uanis(C06F) \\sim Ueq, Uanis(C06G) \\sim Ueq, Uanis(C06H) \\sim Ueq,
Uanis(C06I) \\sim Ueq, Uanis(C06J) \\sim Ueq, Uanis(C60) \\sim Ueq, Uanis(C11)
\\sim Ueq, Uanis(C7) \\sim Ueq, Uanis(C10) \\sim Ueq, Uanis(C3) \\sim Ueq,
Uanis(C52) \\sim Ueq, Uanis(C59) \\sim Ueq, Uanis(O0AA) \\sim Ueq, Uanis(C1AA)
\\sim Ueq, Uanis(C14) \\sim Ueq: with sigma of 0.01 and sigma for terminal
atoms of 0.02
5.a Secondary CH2 refined with riding coordinates:
 C04F(H04G,H04H), C10(H10A,H10B)
5.b Me refined with riding coordinates and stretchable bonds:
 C05A(H05J,H05K,H05L)
5.c Aromatic/amide H refined with riding coordinates:
 C014(H014), C01F(H01F), C01K(H01K), C01L(H01L), C01R(H01R), C01T(H01T),
 C01V(H01V), C01W(H01W), C022(H022), C024(H024), C026(H026), C027(H027),
 C028(H028), C02A(H02A), C02C(H02C), C02D(H02D), C02E(H02E), C02H(H02H),
 C02I(H02I), C02K(H02K), C02L(H02L), C02O(H02O), C02P(H02P), C046(H046),
 C04E(H04E), C2AA(H2AA), C05Y(H05Y), C02X(H02X), C02Z(H02Z), C030(H030),
 C035(H035), C036(H036), C03A(H03A), C03B(H03B), C03D(H03D), C03E(H03E),
 C03H(H03H), C03K(H03K), C03L(H03L), C03N(H03N), C03Q(H03Q), C03T(H03T),
 C03V(H03V), C03W(H03W), C03X(H03X), C03Y(H03Y), C040(H040), C041(H041),
 C049(H049), C04C(H04C), C04D(H04D), C04L(H04L), C04W(H04W), C04X(H04X),
 C05N(H05N), C064(H064), C065(H065), C04Z(H04Z), C050(H050), C052(H052),
 C05D(H05M), C05E(H05O), C05H(H05V), C05I(H05W), C05K(H05X), C05L(H05Z),
 C06F(H06F), C047(H047), C045(H045), C05P(H0AA), C05Q(H1AA), C05R(H3AA),
 C05T(H5AA), C05U(H6AA), C05B(H7AA), C05C(H8AA), C06H(H06H), C05X(H9AA),
 C05Z(H0BA), C062(H062), C063(H063), C066(H066), C069(H069), C067(H067),
 C59(H59), C52(H52), C06A(H06I), C06C(H06M), C06J(H06T)
5.d Fitted hexagon refined as free rotating group:
 C02W(C046,C04E,C17,C2AA,C05Y), C04X(C05N,C15,C064,C065,C04M), C05L(C04Y,C06F,
 C047,C02U,C045), C05U(C05B,C032,C05C,C06H,C60), C069(C04U,C067,C59,C11,C52)
5.e Idealised Me refined as rotating group:
 C03F(H03C,H03F,H03G), C03S(H03I,H03J,H03M), C04N(H04A,H04B,H04F), C055(H05A,
 H05B,H05C), C057(H05D,H05E,H05F), C059(H05G,H05H,H05I), C05F(H05P,H05Q,H05R),
 C05G(H05S,H05T,H05U), C05O(H05,H,HA), C05S(H4AA,HB,HC), C060(H06A,H06B,H06C),
 C061(H06D,H06E,H06G), C06B(H06J,H06K,H06L), C06G(H06N,H06O,H06P), C06I(H06Q,
 H06R,H06S), C7(H7A,H7B,H7C), C3(H3A,H3B,H3C), C31(H31A,H31B,H31C), C1AA(H1AB,
 H1AC,H1AD), C14(H14A,H14B,H14C)
;
_shelx_res_checksum              33954
_shelx_fab_checksum              72558
_platon_squeeze_void_probe_radius 1.20
_olex2_submission_special_instructions 'No special instructions were received'