Pyrene derivatives are among the most widely used organic fluorescent photoprobes. Many of them are photosensitizers for hole injection. Pyrenes, however, are mostly UV absorbers, limiting their utility for photonic applications. Nitration of pyrene shifts its absorption to the visible region. Conversely, nitration of pyrene that is already derivatized for covalent labeling, produces mixtures of isomers that are challenging to separate. We present a robust procedure for attaining isomerically pure nitropyrenes. NMR analysis provides unequivocal assignments of the regioisomers and of the structures of the disubstituted nitropyrenes. The added substituents negligibly affect the electronic properties of the nitropyrenes. Photoexcited nitropyrenes undergo efficient triplet formation, making them an attractive choice for triplet sensitizers and photooxidants. Hence, facile and reliable preparation of disubstituted nitropyrenes provides venues for exploring their electronic and photonic utility.

Photoinduced intramolecular direct arylation allows structurally unique compounds containing phenanthro[9′,10′:4,5]imidazo[1,2-f]phenanthridine and imidazo[1,2-f]phenanthridine skeletons, which mediate excited-state intramolecular proton transfer (ESIPT), to be efficiently synthesized. The developed polycyclic aromatics demonstrate that the combination of five-membered ring structures with a rigid arrangement between a proton donor and a proton acceptor provides a means for attaining large fluorescence quantum yields, exceeding 0.5, even in protic solvents. Steady-state and time-resolved UV/Vis spectroscopy reveals that, upon photoexcitation, the prepared protic heteroaromatics undergo ESIPT, converting them efficiently into their excited-state keto tautomers, which have lifetimes ranging from about 5 to 10 ns. The rigidity of their structures, which suppresses nonradiative decay pathways, is believed to be the underlying reason for the nanosecond lifetimes of these singlet excited states and the observed high fluorescence quantum yields. Hydrogen bonding with protic solvents does not interfere with the excited-state dynamics and, as a result, there is no difference between the occurrences of ESIPT processes in MeOH versus cyclohexane. Acidic media has a more dramatic effect on suppressing ESIPT by protonating the proton acceptor. As a result, in the presence of an acid, a larger proportion of the fluorescence of ESIPT-capable compounds originates from their enol excited states.

Interest in graphene as a two-dimensional quantum-well material for energy applications and nanoelectronics has increased exponentially in the last few years. The recent advances in large-area single-sheet fabrication of pristine graphene have opened unexplored avenues for expanding from nano- to meso-scale applications. The relatively low level of absorptivity and the short lifetimes of excitons of single-sheet graphene suggest that it needs to be coupled with light sensitizers in order to explore its feasibility for photonic applications, such as solar-energy conversion. Red-emitting CdSe quantum dots are employed for photosensitizing single-sheet graphene with areas of several square centimeters. Pyridine coating of the quantum dots not only enhances their adhesion to the graphene surface, but also provides good electronic coupling between the CdSe and the two-dimensional carbon allotrope. Illumination of the quantum dots led to injection of n-carrier in the graphene phase. Time-resolved spectroscopy reveals three modes of photoinduced electron transfer between the quantum dots and the graphene occurring in the femtosecond and picosecond time-domains. Transient absorption spectra provide evidence for photoinduced hole-shift from the CdSe to the pyridine ligands, thereby polarizing the surface of the quantum dots. That is, photoinduced electrical polarization, which favors the simultaneous electron transfer from the CdSe to the graphene phase. These mechanistic insights into the photoinduced interfacial charge transfer have a promising potential to serve as guidelines for the design and development of composites of graphene and inorganic nanomaterials for solar-energy conversion applications.