Research output: Contribution to journal › Article › peer-review
Intramolecular aurophilic interactions in dinuclear gold(i) complexes with twisted bridging 2,2′-bipyridine ligands. / Shmelev, Nikita Y.; Okubazghi, Tesfu H.; Abramov, Pavel A. et al.
In: Dalton Transactions, Vol. 50, No. 36, 28.09.2021, p. 12448-12456.Research output: Contribution to journal › Article › peer-review
}
TY - JOUR
T1 - Intramolecular aurophilic interactions in dinuclear gold(i) complexes with twisted bridging 2,2′-bipyridine ligands
AU - Shmelev, Nikita Y.
AU - Okubazghi, Tesfu H.
AU - Abramov, Pavel A.
AU - Komarov, Vladislav Y.
AU - Rakhmanova, Mariana I.
AU - Novikov, Alexander S.
AU - Gushchin, Artem L.
N1 - Funding Information: Financial support from the Russian Science Foundation (grant no. 21-13-00092) is acknowledged. The authors thank the Ministry of Science and Higher Education of the Russian Federation (grants no. 121031700315-2 and 121031700313-8) for the access to the equipment of the Centre of Collective Usage of NIIC SB RAS. Publisher Copyright: © The Royal Society of Chemistry 2021.
PY - 2021/9/28
Y1 - 2021/9/28
N2 - Elimination of the chloride ion from the [(PPh3)AuCl] complex using silver triflate (AgOTf) in the presence of 2,2′-bipyridine R2bpy (the Au : R2bpy molar ratio is 2 : 1) in dichloromethane at room temperature leads to dinuclear gold(i) complexes [(PPh3Au)2(μ-R2bpy)](OTf)2(R2bpy = bpy (1), dbbpy (2), CH3Obpy (3), 3-CO2CH3bpy (4), 4-CO2CH3bpy (5)) in high yields. The crystal structures for all compounds were determined using X-ray diffraction analysis. In all structures, gold ions are in a typical linear environment, and the bipyridine molecule is twisted, which allows intramolecular aurophilic interactions. Relatively short Au(i)⋯Au(i) contacts (3.1262 (2)-3.400 (1) Å) are found in structures3-5. DFT calculations show the presence of bond critical points (3, −1) for aurophilic interactions in these structures. In structures1and2, the Au(i)⋯Au(i) distances are noticeably larger and equal to 4.479 (1) and 4.589 (1) Å respectively; there are no bond critical points (3, −1) for aurophilic interactions. All complexes show photoluminescence in solid state at room temperature when excited at 300 nm in a wide spectral range: from blue or blue-green emission (400-460 nm) for1-4to orange emission (580 mn) for5. The lifetimes of the excited state are in the microsecond range which is characteristic of phosphorescence. TD-DFT calculations reveal that electronic transitions of different nature are responsible for the photoluminescence of these compounds.
AB - Elimination of the chloride ion from the [(PPh3)AuCl] complex using silver triflate (AgOTf) in the presence of 2,2′-bipyridine R2bpy (the Au : R2bpy molar ratio is 2 : 1) in dichloromethane at room temperature leads to dinuclear gold(i) complexes [(PPh3Au)2(μ-R2bpy)](OTf)2(R2bpy = bpy (1), dbbpy (2), CH3Obpy (3), 3-CO2CH3bpy (4), 4-CO2CH3bpy (5)) in high yields. The crystal structures for all compounds were determined using X-ray diffraction analysis. In all structures, gold ions are in a typical linear environment, and the bipyridine molecule is twisted, which allows intramolecular aurophilic interactions. Relatively short Au(i)⋯Au(i) contacts (3.1262 (2)-3.400 (1) Å) are found in structures3-5. DFT calculations show the presence of bond critical points (3, −1) for aurophilic interactions in these structures. In structures1and2, the Au(i)⋯Au(i) distances are noticeably larger and equal to 4.479 (1) and 4.589 (1) Å respectively; there are no bond critical points (3, −1) for aurophilic interactions. All complexes show photoluminescence in solid state at room temperature when excited at 300 nm in a wide spectral range: from blue or blue-green emission (400-460 nm) for1-4to orange emission (580 mn) for5. The lifetimes of the excited state are in the microsecond range which is characteristic of phosphorescence. TD-DFT calculations reveal that electronic transitions of different nature are responsible for the photoluminescence of these compounds.
UR - http://www.scopus.com/inward/record.url?scp=85115655288&partnerID=8YFLogxK
U2 - 10.1039/d1dt02164h
DO - 10.1039/d1dt02164h
M3 - Article
C2 - 34490869
AN - SCOPUS:85115655288
VL - 50
SP - 12448
EP - 12456
JO - Dalton Transactions
JF - Dalton Transactions
SN - 1477-9226
IS - 36
ER -
ID: 34359919