Influence of ligand variation on the deactivation process of metal-to-ligand charge transfer excited states in quadruply bonded dimolybdenum complexes.

To explore the dynamics of metal-to-ligand charge transfer (MLCT) excited states involving covalently bonded dimetal units, a series of quadruply bonded dimolybdenum (Mo) complexes, namely, [Mo2]-ph, [Mo2]-naph, and [Mo2]-anth, were synthesized and characterized. Our investigations reveal a non-radiative process associated with the deactivation of the MLCT state into a low-lying dimetal-centered triplet state (Mo-δδ*), resulting in the populated MLCT states in these molecular systems exhibiting either extremely weak emission or being non-emissive. The influence of ligand variation on the dynamics of MLCT states was examined using femtosecond transient absorption spectroscopy, with deactivation time constants determined to be 1.

A stronger acceptor decreases the rates of charge transfer: ultrafast dynamics and on/off switching of charge separation in organometallic donor-bridge-acceptor systems.

To unravel the role of driving force and structural changes in directing the photoinduced pathways in donor-bridge-acceptor (DBA) systems, we compared the ultrafast dynamics in novel DBAs which share a phenothiazine (PTZ) electron donor and a Pt(ii) -acetylide bridge (-C[triple bond, length as m-dash]C-Pt-C[triple bond, length as m-dash]C-), but bear different acceptors conjugated into the bridge (naphthalene-diimide, NDI; or naphthalene-monoimide, NAP). The excited state dynamics were elucidated by transient absorption, time-resolved infrared (TRIR, directly following electron density changes on the bridge/acceptor), and broadband fluorescence-upconversion (FLUP, directly following sub-picosecond intersystem crossing) spectroscopies, supported by TDDFT calculations. Direct conjugation of a strong acceptor into the bridge leads to switching of the lowest excited state from the intraligand IL state to the desired charge-separated CSS state.

Direct Determination of the Rate of Intersystem Crossing in a Near-IR Luminescent Cr(III) Triazolyl Complex.

A detailed understanding of the dynamics of photoinduced processes occurring in the electronic excited state is essential in informing the rational design of photoactive transition-metal complexes. Here, the rate of intersystem crossing in a Cr(III)-centered spin-flip emitter is directly determined through the use of ultrafast broadband fluorescence upconversion spectroscopy (FLUPS). In this contribution, we combine 1,2,3-triazole-based ligands with a Cr(III) center and report the solution-stable complex [Cr(btmp)] (btmp = 2,6-(4-phenyl-1,2,3-triazol-1-yl-methyl)pyridine) (), which displays near-infrared (NIR) luminescence at 760 nm (τ = 13.