Although vibronic coupling phenomena have been recognized in the excite state dynamics of transition metal complexes, its impact on photoinduced electron transfer (PET) remains largely unexplored. This study investigates coherent wavepacket (CWP) dynamics during PET processes in a covalently linked electron donor-acceptor complex featuring a cyclometalated Pt(ii) dimer as the donor and naphthalene diimide (NDI) as the acceptors. Upon photoexciting the Pt(ii) dimer electron donor, ultrafast broadband transient absorption spectroscopy revealed direct modulation of NDI radical anion formation through certain CWP motions and correlated temporal evolutions of the amplitudes for these CWPs with the NDI radical anion formation.
View Article and Find Full Text PDFDesign-specific control over the transitions between excited electronic states with different spin multiplicities is of the utmost importance in molecular and materials chemistry. Previous studies have indicated that the combination of spin-orbit and vibronic effects, collectively termed the spin-vibronic effect, can accelerate quantum-mechanically forbidden transitions at non-adiabatic crossings. However, it has been difficult to identify precise experimental manifestations of the spin-vibronic mechanism.
View Article and Find Full Text PDFDinuclear d Pt(II) complexes, where two mononuclear square planar Pt(II) units are bridged in an "A-frame" geometry, possess photophysical properties characterised by either metal-to-ligand-(MLCT) or metal-metal-ligand-to-ligand charge transfer (MMLCT) transitions determined by the distance between the two Pt(II) centres. When using 8-hydroxyquinoline (8HQH) as the bridging ligand to construct novel dinuclear complexes with general formula [C^NPt(μ-8HQ)], where C^N is either 2-phenylpyridine (1) or 7,8-benzoquinoline (2), triplet ligand-centered (LC) photophysics results echoing that in a mononuclear model chromophore, [Pt(8HQ)] (3). The lengthened Pt-Pt distances of 3.
View Article and Find Full Text PDFFour Cu(I) (phenanthroline) photosensitizers formulated from a new ligand structural motif () coded according to their 2,9-substituents were synthesized, structurally characterized, and fully evaluated using steady-state and time-resolved absorption and photoluminescence (PL) measurements as well as electrochemistry. The 2,9-disubstituted-3,4,7,8-tetramethyl-1,10-phenanthroline ligands feature the following six-membered ring systems prepared through photochemical synthesis: 4,4-dimethylcyclohexyl (), tetrahydro-2H-pyran-4-yl ), tetrahydro-2H-thiopyran-4-yl (), and 4,4-difluorocyclohexyl (). Universally, these Cu(I) metal-to-ligand charge transfer (MLCT) chromophores display excited-state lifetimes on the microsecond time scale at room temperature, including the three longest-lived homoleptic cuprous phenanthroline excited states measured to date in de-aerated CHCl, τ = 2.
View Article and Find Full Text PDFBackground: Here, we review our experience of providing inpatient infectious disease (ID) consultations using real-time interactive telemedicine assessments. We sought to obtain a baseline and document trends regarding the use of telemedicine ID (teleID) consults as an adjunct to the standard of care through the time period in which teleID consultations were introduced.
Methods: Data were pulled via manual, retrospective chart reviews of the electronic medical record.