Isolating single molecules in the solid state has allowed fundamental experiments in basic and applied sciences. When cooled down to liquid helium temperature, certain molecules show transition lines, that are tens of megahertz wide, limited only by the excited state lifetime. The extreme flexibility in the synthesis of organic materials provides, at low costs, a wide palette of emission wavelengths and supporting matrices for such single chromophores. In the last decades, the controlled coupling to photonic structures has led to an optimized interaction efficiency with light. Molecules can hence be operated as single photon sources and as non-linear elements with competitive performance in terms of coherence, scalability and compatibility with diverse integrated platforms. Moreover, they can be used as transducers for the optical read-out of fields and material properties, with the promise of single-quanta resolution in the sensing of charges and motion. We show that quantum emitters based on single molecules hold promise to play a key role in the development of quantum science and technologies.Modern societies have an ever-growing need for efficient computation techniques and for fast and secure communication, to distribute a huge amount of data around the globe. By harnessing quantum effects present at the nanoscale, new quantum technologies can be employed to meet these needs, including quantum cryptography and fully-fledged quantum information processing. On the other hand, the extreme sensitivity of quantum systems to their local environment can be exploited to also create new sensing devices, which provide unprecedented precision, accuracy and resolution and can be deployed within large quantum networks. Key applications require the generation and manipulation of quantum states of light, such as photonic quantum simulation [1, 2], linear optical quantum computing [3], device-independent or long-distance quantum key distribution protocols [4], sub-shot-noise imaging [5] and quantum metrology [6,7]. In this context, single impurities in solid-state systems can act as bright, on-demand single-photon sources (SPSs), which are a crucial resource in these photonic quantum technologies. Quantum emitters may also perform as non-linear elements at the few-photon level [8] and as nanoscale sensors, allowing the optical read-out of local properties of materials and fields. In this context, single molecules in the solid-state offer competitive and reliable properties, with several key advantages. First, they are very small and have well-defined transition dipole moments so that they can be used as nanoscopic sensors for a number of scalar and vector quantities such as pressure, strain, temperature, electric and magnetic fields, as well as optical fields. Second, organic molecules can be designed and synthesized for different parts of the visible spectrum and integrated in a range of organic matrices, a feature that is a severe limiting factor for color centers in diamond or lithographically produced semiconductor quan...

Electron-deficient π-conjugated functional dyes lie at the heart of organic optoelectronics. Adding nitro groups to aromatic compounds usually quenches their fluorescence via inter-system crossing (ISC) or internal conversion (IC). While strong electronic coupling of the nitro groups with the dyes ensures the benefits from these electron-withdrawing substituents, it also leads to fluorescence quenching. Here, we demonstrate how such electronic coupling affects the photophysics of acceptor–donor–acceptor fluorescent dyes, with nitrophenyl acceptors and a pyrrolo[3,2-b]pyrrole donor. The position of the nitro groups and the donor-acceptor distance strongly affect the fluorescence properties of the bis-nitrotetraphenylpyrrolopyrroles. Concurrently, increasing solvent polarity quenches the emission that recovers upon solidifying the media. Intramolecular charge transfer (CT) and molecular dynamics, therefore, govern the fluorescence of these nitro-aromatics. While balanced donor-acceptor coupling ensures fast radiative deactivation and slow ISC essential for large fluorescence quantum yields, vibronic borrowing accounts for medium dependent IC via back CT. These mechanistic paradigms set important design principles for molecular photonics and electronics.

Red-emissive dyes based on a previously unknown skeleton--dipyrrolo[1,2-b:1',2'-g][2,6]naphthyridine-5,11-dione--can be easily synthesized from simple and inexpensive reagents by one- or two-step routes. A careful selection of the substituents gives access to a variety of dipyrrolonaphthyridinedione derivatives with intense fluorescence in the range of 520-740 nm.

The crystal structure of 2-butylamino-6-methyl-4-nitropyridine N-oxide (2B6M) was resolved on the basis of X-ray diffraction. Solid 2B6M occurs in the form of a doubly hydrogen-bonded dimer with squarelike hydrogen-bonding network composed of two intra- (2.556(2) A) and two intermolecular (2.891(2) A) N-H...O type hydrogen bonds. The molecule thus has both a protonable and a deprotonable group that led us to investigate the possibility of an excited-state proton transfer (ESIPT) reaction in different solvents by means of experimental absorption, steady state, and time-resolved emission spectroscopy. The results were correlated with quantum mechanical TD-DFT and PM3 calculations. Experimental and theoretical findings show the possibility of an ESIPT reaction in polar solvents. It is demonstrated that in particular the emission spectra of 2B6M are very sensitive to solvent properties, and a large value of the Stokes shift (about 8000 cm(-1)) in acetonitrile is indicative for an ESIPT process. This conclusion is further supported by time-resolved fluorescence decay measurents that show dual exponential decay in polar solvents. Vertical excitation energies calculated by TD-DFT reproduce the experimental absorption maxima in nonpolar solvents well. The majority of electronic transitions in 2B6M is of pi --> pi* character with a charge shift from the electron-donating to the electron-accepting groups. The calculations show that, due to the charge redistribution on excitation, the acidity of the amino group increases significantly, which facilitates the proton transfer from the amino to the N-oxide group in the excited state.

Absorption and fluorescence from single molecules can be tuned by applying an external electric field – a phenomenon known as the Stark effect. A linear Stark effect is associated to a lack of centrosymmetry of the guest in the host matrix. Centrosymmetric guests can display a linear Stark effect in disordered matrices, but the response of individual guest molecules is often relatively weak and non‐uniform, with a broad distribution of the Stark coefficients. Here we introduce a novel single‐molecule host‐guest system, dibenzoterrylene (DBT) in 2,3‐dibromonaphthalene (DBN) crystal. Fluorescent DBT molecules show excellent spectral stability with a large linear Stark effect, of the order of 1.5 GHz/kVcm −1 , corresponding to an electric dipole moment change of around 2 D. Remarkably, when the electric field is aligned with the a crystal axis, nearly all DBT molecules show either positive or negative Stark shifts with similar absolute values. These results are consistent with quantum chemistry calculations. Those indicate that DBT substitutes three DBN molecules along the a ‐axis, giving rise to eight equivalent embedding sites, related by the three glide planes of the orthorhombic crystal. The static dipole moment of DBT molecules is created by host‐induced breaking of the inversion symmetry. This new host–guest system is promising for applications that require a high sensitivity of fluorescent emitters to electric fields, for example to probe weak electric fields.

Fluorescence and fluorescence excitation spectra of terrylene deposited in Ne and Ar matrixes at 7 K have been studied. The (0,0) fluorescence band of terrylene in Ne matrixes is shifted by 330 cm-1 to low energy with respect to the (0,0) fluorescence excitation band observed at 18990 cm-1. Furthermore, the vibronic structures of both spectra are different. In contrary to this observation, the fluorescence and fluorescence excitation spectra of terrylene in Ar matrixes have a common origin at 18312 cm-1 and demonstrate mirror symmetry. Semiempirical AM1 calculations combined with the analysis of the vibronic structure of the spectra suggest that terrylene molecules in the excited S1 state are subject to relaxation. This relaxation is possible in soft Ne but it is frozen in rigid Ar matrix.

No abstract

We have unraveled the effects of an amino substituent in the ortho position on the excited-state dynamics of 4-nitropyridine N-oxide by studying the picosecond fluorescence kinetics and femtosecond transient absorption of a newly synthesized compound, 2-butylamino-6-methyl-4-nitropyridine N-oxide, and by quantum chemical calculations. Similar to the parent compound, the S(1) state of the target molecule has significant charge-transfer character and shows a large (approximately 8000 cm(-1)) static Stokes shift in acetonitrile. Analysis of the experimental and the theoretical results leads, however, to a new scenario in which this intramolecular charge transfer triggers in polar, aprotic solvents an ultrafast (around 100 fs) intramolecular proton transfer between the amino and the N-O group. The electronically excited N-OH tautomer is subsequently subject to solvent relaxation and decays with a lifetime of approximately 150 ps to the ground state.