Time-dependent density functional theory study of the luminescence properties of gold phosphine thiolate complexes

The Journal of Physical Chemistry. a
Emilie B Guidez, Christine M Aikens

Abstract

The origin of the emission of the gold phosphine thiolate complex (TPA)AuSCH(CH3)2 (TPA = 1,3,5-triaza-7-phosphaadamantanetriylphosphine) is investigated using time-dependent density functional theory (TDDFT). This system absorbs light at 3.6 eV, which corresponds mostly to a ligand-to-metal transition with some interligand character. The P-Au-S angle decreases upon relaxation in the S1 and T1 states. Our calculations show that these two states are strongly spin-orbit coupled at the ground state geometry. Ligand effects on the optical properties of this complex are also discussed by looking at the simple AuP(CH3)3SCH3 complex. The excitation energies differ by several tenths of an electronvolt. Excited state optimizations show that the excited singlet and triplet of the (TPA)AuSCH(CH3)2 complex are bent. On the other hand, the Au-S bond breaks in the excited state for the simple complex, and TDDFT is no longer an adequate method. The excited state energy landscape of gold phosphine thiolate systems is very complex, with several state crossings. This study also shows that the formation of the [(TPA)AuSCH(CH3)2]2 dimer is favorable in the ground state. The inclusion of dispersion interactions in the calculations affects the optim...Continue Reading

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Citations

Aug 16, 2016·Journal of the American Chemical Society·K L Dimuthu M Weerawardene, Christine M Aikens
Mar 1, 2018·Annual Review of Physical Chemistry·K L Dimuthu M WeerawardeneChristine M Aikens
May 15, 2018·Dalton Transactions : an International Journal of Inorganic Chemistry·Masahisa OsawaMunetaka Akita
Aug 28, 2019·Scientific Reports·Jong Hyun KimSamuel G Awuah
Nov 11, 2020·Dalton Transactions : an International Journal of Inorganic Chemistry·Masahisa OsawaMunetaka Akita
Nov 5, 2019·Journal of the American Chemical Society·K L Dimuthu M WeerawardeneChristine M Aikens

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