Luminescence color alteration induced by trapped solvent molecules in crystals of tetrahedral gold(i) complexes: near-unity luminescence mixed with thermally activated delayed fluorescence and phosphorescence.
Osawa, Masahisa; Yamayoshi, Hiroto; Hoshino, Mikio; Tanaka, Yuya; Akita, Munetaka; Dalton transactions (Cambridge, England : 2003) 48 (2019) 9094–9103; doi:10.1039/c9dt01373c

data_7049975
_publ_section_title
;
 Luminescence color alteration induced by trapped solvent molecules in
 crystals of tetrahedral gold(i) complexes: near-unity luminescence mixed
 with thermally activated delayed fluorescence and phosphorescence.
;
_journal_issue                   25
_journal_name_full
'Dalton transactions (Cambridge, England : 2003)'
_journal_page_first              9094
_journal_page_last               9103
_journal_paper_doi               10.1039/c9dt01373c
_journal_volume                  48
_journal_year                    2019
_chemical_formula_moiety         '2(C92 H112 Au P4), 2(Cl), 5(O), 3(C H2 Cl2)'
_chemical_formula_sum            'C187 H230 Au2 Cl8 O5 P8'
_chemical_formula_weight         3483.02
_space_group_crystal_system      triclinic
_space_group_IT_number           2
_space_group_name_Hall           '-P 1'
_space_group_name_H-M_alt        'P -1'
_symmetry_space_group_name_Hall  '-P 1'
_symmetry_space_group_name_H-M   'P -1'
_atom_sites_solution_hydrogens   geom
_audit_creation_date             2019-01-08
_audit_creation_method
;
Olex2 1.2
(compiled May 18 2018 14:05:52 for OlexSys, GUI svn.r5506)
;
_audit_update_record
;
2019-03-12 deposited with the CCDC.    2019-05-06 downloaded from the CCDC.
;
_cell_angle_alpha                100.322(2)
_cell_angle_beta                 106.859(2)
_cell_angle_gamma                111.240(2)
_cell_formula_units_Z            1
_cell_length_a                   15.891(2)
_cell_length_b                   17.780(3)
_cell_length_c                   19.707(3)
_cell_measurement_reflns_used    9982
_cell_measurement_temperature    90(2)
_cell_measurement_theta_max      28.02
_cell_measurement_theta_min      2.19
_cell_volume                     4707.9(12)
_computing_cell_refinement       'SAINT V8.38A (?, 2016)'
_computing_data_reduction        'SAINT V8.38A (?, 2016)'
_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    'SHELXT 2014/5 (Sheldrick, 2014)'
_diffrn_ambient_temperature      90(2)
_diffrn_measured_fraction_theta_full 0.982
_diffrn_measured_fraction_theta_max 0.982
_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  0.0240
_diffrn_reflns_av_unetI/netI     0.0500
_diffrn_reflns_Laue_measured_fraction_full 0.982
_diffrn_reflns_Laue_measured_fraction_max 0.982
_diffrn_reflns_limit_h_max       14
_diffrn_reflns_limit_h_min       -18
_diffrn_reflns_limit_k_max       21
_diffrn_reflns_limit_k_min       -21
_diffrn_reflns_limit_l_max       23
_diffrn_reflns_limit_l_min       -22
_diffrn_reflns_number            22535
_diffrn_reflns_point_group_measured_fraction_full 0.982
_diffrn_reflns_point_group_measured_fraction_max 0.982
_diffrn_reflns_theta_full        25.026
_diffrn_reflns_theta_max         25.026
_diffrn_reflns_theta_min         1.296
_diffrn_standards_number         0
_exptl_absorpt_coefficient_mu    1.788
_exptl_absorpt_correction_T_max  0.931
_exptl_absorpt_correction_T_min  0.796
_exptl_absorpt_correction_type   multi-scan
_exptl_absorpt_process_details
;
SADABS-2016/2 (Bruker,2016) was used for absorption correction.
wR2(int) was 0.0920 before and 0.0328 after correction.
The Ratio of minimum to maximum transmission is 0.7923.
The \l/2 correction factor is Not present.
;
_exptl_crystal_colour            'light yellow'
_exptl_crystal_colour_modifier   light
_exptl_crystal_colour_primary    yellow
_exptl_crystal_density_diffrn    1.229
_exptl_crystal_description       plate
_exptl_crystal_F_000             1806
_exptl_crystal_size_max          0.13
_exptl_crystal_size_mid          0.12
_exptl_crystal_size_min          0.04
_refine_diff_density_max         3.448
_refine_diff_density_min         -2.016
_refine_diff_density_rms         0.147
_refine_ls_extinction_method     none
_refine_ls_goodness_of_fit_ref   1.035
_refine_ls_hydrogen_treatment    constr
_refine_ls_matrix_type           full
_refine_ls_number_parameters     1096
_refine_ls_number_reflns         16621
_refine_ls_number_restraints     246
_refine_ls_restrained_S_all      1.069
_refine_ls_R_factor_all          0.0631
_refine_ls_R_factor_gt           0.0541
_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^)+(0.0881P)^2^+21.5938P] where P=(Fo^2^+2Fc^2^)/3'
_refine_ls_weighting_scheme      calc
_refine_ls_wR_factor_gt          0.1443
_refine_ls_wR_factor_ref         0.1514
_reflns_Friedel_coverage         0.000
_reflns_number_gt                14340
_reflns_number_total             16621
_reflns_threshold_expression     'I > 2\s(I)'
_cod_data_source_file            c9dt01373c2.cif
_cod_data_source_block           1YL
_cod_depositor_comments
'Adding full bibliography for 7049974--7049976.cif.'
_cod_database_code               7049975
_shelx_shelxl_version_number     2018/3
_shelx_estimated_absorpt_t_max   0.932
_shelx_estimated_absorpt_t_min   0.801
_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
 C70-C69
 1.54 with sigma of 0.02
 C69-C72
 1.54 with sigma of 0.02
 C69-C71
 1.54 with sigma of 0.02
 C81-C84
 1.54 with sigma of 0.02
 C81-C82
 1.54 with sigma of 0.02
 C81-C83
 1.54 with sigma of 0.02
 C73-C75
 1.54 with sigma of 0.02
 C73-C76
 1.54 with sigma of 0.02
 C73-C74
 1.54 with sigma of 0.02
 Cl2-C93
 1.8 with sigma of 0.02
 Cl3-C93
 1.8 with sigma of 0.02
 C94-Cl4
 1.8 with sigma of 0.02
 C94-Cl0A
 1.8 with sigma of 0.02
 C70-C72
 2.54 with sigma of 0.04
 C72-C71
 2.54 with sigma of 0.04
 C71-C70
 2.54 with sigma of 0.04
 C83-C84
 2.54 with sigma of 0.04
 C84-C82
 2.54 with sigma of 0.04
 C82-C83
 2.54 with sigma of 0.04
 C83A-C84A
 2.54 with sigma of 0.04
 C84A-C82A
 2.54 with sigma of 0.04
 C82A-C83A
 2.54 with sigma of 0.04
 C75-C76
 2.54 with sigma of 0.04
 C76-C74
 2.54 with sigma of 0.04
 C75-C74
 2.54 with sigma of 0.04
 C74A-C75A
 2.54 with sigma of 0.04
 C75A-C76A
 2.54 with sigma of 0.04
 C76A-C74A
 2.54 with sigma of 0.04
 Cl2-Cl3
 3.2 with sigma of 0.04
 Cl0A-Cl4
 3.2 with sigma of 0.04
 C92A-C90A
 2.54 with sigma of 0.04
 C92A-C91A
 2.54 with sigma of 0.04
 C91A-C90A
 2.54 with sigma of 0.04
 C90-C91
 2.54 with sigma of 0.04
 C91-C92
 2.54 with sigma of 0.04
 C90-C92
 2.54 with sigma of 0.04
 C70-C69 \\sim C70A-C69
 with sigma of 0.02
 C69-C71 \\sim C69-C71A
 with sigma of 0.02
 C69-C72 \\sim C69-C72A
 with sigma of 0.02
 C81-C82 \\sim C81-C82A
 with sigma of 0.02
 C81-C84 \\sim C81-C84A
 with sigma of 0.02
 C81-C83 \\sim C81-C83A
 with sigma of 0.02
 C73-C76 \\sim C73-C76A
 with sigma of 0.02
 C73-C74 \\sim C73-C74A
 with sigma of 0.02
 C73-C75 \\sim C73-C75A
 with sigma of 0.02
 C89-C92 \\sim C89-C92A
 with sigma of 0.02
 C89-C90 \\sim C89-C90A
 with sigma of 0.02
 C89-C91 \\sim C89-C91A
 with sigma of 0.02
3. Uiso/Uaniso restraints and constraints
Uanis(C75) \\sim Ueq, Uanis(C75A) \\sim Ueq, Uanis(C76A) \\sim Ueq, Uanis(C76)
\\sim Ueq, Uanis(C74) \\sim Ueq, Uanis(C74A) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C83A) \\sim Ueq, Uanis(C83) \\sim Ueq, Uanis(C82) \\sim Ueq, Uanis(C82A)
\\sim Ueq, Uanis(C84A) \\sim Ueq, Uanis(C84) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(C70A) \\sim Ueq, Uanis(C70) \\sim Ueq, Uanis(C71) \\sim Ueq, Uanis(C71A)
\\sim Ueq, Uanis(C72) \\sim Ueq, Uanis(C72A) \\sim Ueq: with sigma of 0.01 and
sigma for terminal atoms of 0.02
Uanis(O1A) \\sim Ueq, Uanis(O1) \\sim Ueq: with sigma of 0.01 and sigma for
terminal atoms of 0.02
Uanis(C92) \\sim Ueq, Uanis(C91) \\sim Ueq, Uanis(C90) \\sim Ueq: with sigma of
0.01 and sigma for terminal atoms of 0.02
Uanis(C90A) \\sim Ueq, Uanis(C91A) \\sim Ueq, Uanis(C92A) \\sim Ueq: with sigma
of 0.01 and sigma for terminal atoms of 0.02
Uanis(O1A) \\sim Ueq, Uanis(Cl0A) \\sim Ueq, Uanis(Cl4) \\sim Ueq, Uanis(C94)
\\sim Ueq, Uanis(Cl2) \\sim Ueq, Uanis(C93) \\sim Ueq, Uanis(Cl3) \\sim Ueq:
with sigma of 0.01 and sigma for terminal atoms of 0.02
Uanis(O2) \\sim Ueq: with sigma of 0.005 and sigma for terminal atoms of 0.01
4. Others
 Sof(Cl1A)=1-FVAR(1)
 Sof(Cl1)=FVAR(1)
 Sof(O1A)=1-FVAR(2)
 Sof(O1)=FVAR(2)
 Sof(C70A)=Sof(H70D)=Sof(H70E)=Sof(H70F)=Sof(C72A)=Sof(H72D)=Sof(H72E)=
 Sof(H72F)=Sof(C71A)=Sof(H71D)=Sof(H71E)=Sof(H71F)=1-FVAR(3)
 Sof(C70)=Sof(H70A)=Sof(H70B)=Sof(H70C)=Sof(C71)=Sof(H71A)=Sof(H71B)=Sof(H71C)=
 Sof(C72)=Sof(H72A)=Sof(H72B)=Sof(H72C)=FVAR(3)
 Sof(C83A)=Sof(H83D)=Sof(H83E)=Sof(H83F)=Sof(C84A)=Sof(H84D)=Sof(H84E)=
 Sof(H84F)=Sof(C82A)=Sof(H82D)=Sof(H82E)=Sof(H82F)=1-FVAR(4)
 Sof(C83)=Sof(H83A)=Sof(H83B)=Sof(H83C)=Sof(C82)=Sof(H82A)=Sof(H82B)=Sof(H82C)=
 Sof(C84)=Sof(H84A)=Sof(H84B)=Sof(H84C)=FVAR(4)
 Sof(C75A)=Sof(H75D)=Sof(H75E)=Sof(H75F)=Sof(C76A)=Sof(H76D)=Sof(H76E)=
 Sof(H76F)=Sof(C74A)=Sof(H74D)=Sof(H74E)=Sof(H74F)=1-FVAR(5)
 Sof(C76)=Sof(H76A)=Sof(H76B)=Sof(H76C)=Sof(C74)=Sof(H74A)=Sof(H74B)=Sof(H74C)=
 Sof(C75)=Sof(H75A)=Sof(H75B)=Sof(H75C)=FVAR(5)
 Sof(C90A)=Sof(H90D)=Sof(H90E)=Sof(H90F)=Sof(C91A)=Sof(H91D)=Sof(H91E)=
 Sof(H91F)=Sof(C92A)=Sof(H92D)=Sof(H92E)=Sof(H92F)=1-FVAR(6)
 Sof(C90)=Sof(H90A)=Sof(H90B)=Sof(H90C)=Sof(C92)=Sof(H92A)=Sof(H92B)=Sof(H92C)=
 Sof(C91)=Sof(H91A)=Sof(H91B)=Sof(H91C)=FVAR(6)
 Fixed Sof: Cl0A(0.5) Cl4(0.5) C94(0.5) H94A(0.5) H94B(0.5) O0AA(0.5)
5.a Secondary CH2 refined with riding coordinates:
 C93(H93A,H93B), C94(H94A,H94B)
5.b Me refined with riding coordinates:
 C67(H67A,H67B,H67C), C62(H62A,H62B,H62C), C68(H68A,H68B,H68C), C63(H63A,H63B,
 H63C), C66(H66A,H66B,H66C), C70(H70A,H70B,H70C), C64(H64A,H64B,H64C), C80(H80A,
 H80B,H80C), C78(H78A,H78B,H78C), C86(H86A,H86B,H86C), C79(H79A,H79B,H79C),
 C76(H76A,H76B,H76C), C87(H87A,H87B,H87C), C88(H88A,H88B,H88C), C83(H83A,H83B,
 H83C), C90(H90A,H90B,H90C), C82(H82A,H82B,H82C), C84(H84A,H84B,H84C), C92(H92A,
 H92B,H92C), C91(H91A,H91B,H91C), C71(H71A,H71B,H71C), C72(H72A,H72B,H72C),
 C74(H74A,H74B,H74C), C75(H75A,H75B,H75C), C70A(H70D,H70E,H70F), C72A(H72D,H72E,
 H72F), C71A(H71D,H71E,H71F), C83A(H83D,H83E,H83F), C84A(H84D,H84E,H84F),
 C82A(H82D,H82E,H82F), C75A(H75D,H75E,H75F), C76A(H76D,H76E,H76F), C74A(H74D,
 H74E,H74F), C90A(H90D,H90E,H90F), C91A(H91D,H91E,H91F), C92A(H92D,H92E,H92F)
5.c Aromatic/amide H refined with riding coordinates:
 C47(H47), C44(H44), C11(H11), C46(H46), C45(H45), C32(H32), C30(H30),
 C56(H56), C12(H12), C57(H57), C17(H17), C59(H59), C24(H24), C26(H26), C14(H14),
  C8(H8), C33(H33), C16(H16), C54(H54), C60(H60), C42(H42), C6(H6), C9(H9),
 C41(H41), C50(H50), C20(H20), C15(H15), C3(H3), C38(H38), C23(H23), C27(H27),
 C53(H53), C2(H2), C29(H29), C35(H35), C36(H36), C39(H39), C5(H5), C51(H51),
 C21(H21)
;
_olex2_submission_special_instructions 'No special instructions were received'