TY - JOUR

T1 - Just Add the Gold: Aggregation-Induced-Emission Properties of Alkynylphosphinegold(I) Complexes Functionalized with Phenylene-Terpyridine Subunits

AU - Abramova, Evgenia O.

AU - Paderina, Aleksandra V.

AU - Slavova, Sofia O.

AU - Kostenko, Ekaterina A.

AU - Eliseenkov, Eugene V.

AU - Petrovskii, Stanislav K.

AU - Gitlina, Anastasia Yu

AU - Boyarskiy, Vadim P.

AU - Grachova, Elena V.

N1 - Publisher Copyright: © 2021 American Chemical Society.

PY - 2021/11/26

Y1 - 2021/11/26

N2 - A series of organometallic complexes containing an alkynylphosphinegold(I) fragment and a phenylene-terpyridine moiety connected together by flexible linker have been prepared using the specially designed terpyridine ligands. The compounds were studied crystallographically to reveal that all of them contain a linearly coordinated Au(I) atom and a free terpyridine moiety. The different orientations of the molecules relative to each other in the solid state determine the multiple noncovalent interactions such as antiparallel ππstacking, CH-π, and CH-Au, but no aurophilic interactions are realized. The organometallic Au(I) complexes obtained show fluorescence in the solution and dual singlet-triplet emission in the solid state. This means that their photophysical behavior is determined by both intermolecular lattice-defined interactions and Au(I) atom introduction. Density functional theory computational analysis supported the assignment of emission to intraligand electronic transitions only inside the phenylene-terpyridine part with no Au(I) involved. In addition, a study of the nature of the excited states for the "dimer"with an antiparallel orientation of the terpyridine fragment showed that this orientation leads to the generation of abstracted singlet and triplet states, lowering their energy in comparison with the monomer complex. Thus, the complexes obtained can be qualified as examples of Au(I)-containing organometallic aggregation-induced-emission luminogens.

AB - A series of organometallic complexes containing an alkynylphosphinegold(I) fragment and a phenylene-terpyridine moiety connected together by flexible linker have been prepared using the specially designed terpyridine ligands. The compounds were studied crystallographically to reveal that all of them contain a linearly coordinated Au(I) atom and a free terpyridine moiety. The different orientations of the molecules relative to each other in the solid state determine the multiple noncovalent interactions such as antiparallel ππstacking, CH-π, and CH-Au, but no aurophilic interactions are realized. The organometallic Au(I) complexes obtained show fluorescence in the solution and dual singlet-triplet emission in the solid state. This means that their photophysical behavior is determined by both intermolecular lattice-defined interactions and Au(I) atom introduction. Density functional theory computational analysis supported the assignment of emission to intraligand electronic transitions only inside the phenylene-terpyridine part with no Au(I) involved. In addition, a study of the nature of the excited states for the "dimer"with an antiparallel orientation of the terpyridine fragment showed that this orientation leads to the generation of abstracted singlet and triplet states, lowering their energy in comparison with the monomer complex. Thus, the complexes obtained can be qualified as examples of Au(I)-containing organometallic aggregation-induced-emission luminogens.

UR - http://www.scopus.com/inward/record.url?scp=85120548737&partnerID=8YFLogxK

UR - https://www.mendeley.com/catalogue/3372214b-3f9a-309e-8a87-e5a91ee5f93d/

U2 - 10.1021/acs.inorgchem.1c02125

DO - 10.1021/acs.inorgchem.1c02125

M3 - Article

AN - SCOPUS:85120548737

VL - 60

SP - 18715

EP - 18725

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 24

ER -