TY - JOUR

T1 - Homoleptic Alkynylpyridinium Au(I) Complexes as Organometallic ‘D-π-A’ Chromophores

AU - Петровский, Станислав Константинович

AU - Петровская, Алина Дмитриевна

AU - Сизова, Анастасия Андреевна

AU - Сизов, Владимир Викторович

AU - Грачева, Елена Валерьевна

PY - 2023/7/1

Y1 - 2023/7/1

N2 - A series of terminal acetylenes bearing methylpyridinium acceptor group attached to the alkynyl unit with different π-conjugated aromatic linker have been synthetized. These alkynylpyridinium salts are efficient ‘push-pull’ chromophores demonstrating bright UV-vis fluorescence with quantum yields up to 70 %. The homoleptic bis-alkynyl Au(I) complexes based on these alkynylpyridinium ligands demonstrate complicated photophysical behavior including dual emission in solution. The variation of the linker allows one to tune the intrasystem charge transfer and thus to change the electronic and photophysical properties of the organogold ‘D-π-A’ system. This study demonstrates that absolute and relative intensities of the bands in emission spectra and their energies are responsive to solvent system and anion nature even in case of weakly coordinative anions. TDDFT calculations show that the transitions related to emission of the complex cations are strongly associated with the hybrid MLCT/ILCT charge transfer, thus demonstrating that the complex molecule acts as a unified ‘D-π-A’ system.

AB - A series of terminal acetylenes bearing methylpyridinium acceptor group attached to the alkynyl unit with different π-conjugated aromatic linker have been synthetized. These alkynylpyridinium salts are efficient ‘push-pull’ chromophores demonstrating bright UV-vis fluorescence with quantum yields up to 70 %. The homoleptic bis-alkynyl Au(I) complexes based on these alkynylpyridinium ligands demonstrate complicated photophysical behavior including dual emission in solution. The variation of the linker allows one to tune the intrasystem charge transfer and thus to change the electronic and photophysical properties of the organogold ‘D-π-A’ system. This study demonstrates that absolute and relative intensities of the bands in emission spectra and their energies are responsive to solvent system and anion nature even in case of weakly coordinative anions. TDDFT calculations show that the transitions related to emission of the complex cations are strongly associated with the hybrid MLCT/ILCT charge transfer, thus demonstrating that the complex molecule acts as a unified ‘D-π-A’ system.

KW - Aklynyl complexes

KW - Gold

KW - Luminescence

KW - Pyridinium salts

KW - TDDFT calculations

UR - https://www.mendeley.com/catalogue/657c0bf3-c23e-3957-bf38-4a31f013f0d5/

U2 - 10.1002/cplu.202300155

DO - 10.1002/cplu.202300155

M3 - Article

VL - 88

JO - ChemPlusChem

JF - ChemPlusChem

SN - 2192-6506

IS - 7

M1 - e202300155

ER -