Vânia F. Pais

Information processing with molecules--Quo vadis?

Information processing at the molecular level is coming of age. Since the first molecular AND gate was proposed about 20 years ago, the molecular interpretation of binary logic has become vastly more sophisticated and complex. However, the field is also at a crossroads. While cleverly designed molecular building blocks are abundant, difficult questions remain. How can molecular components be flexibly assembled into larger circuits, and how can these components communicate with one another. The concept of all-photonic switching with photochromic supermolecules has shown some interesting potential and is discussed in this review. Although the field of molecular logic was originally discussed mainly in terms of a technology that might compete with solid-state computers, potential applications have expanded to include clever molecular systems and materials for drug delivery, sensing, probing, encoding, and diagnostics. These upcoming trends, which are herein illustrated by selected examples, deserve general attention.

OFF-ON-OFF fluorescence switch with T-latch function.

A novel molecular system with characteristics of an OFF-ON-OFF fluorescence switch was designed to integrate the function of a T-latch. In detail, a receptor1-fluorophore-receptor2 architecture was adopted to achieve fluorescence switching upon addition of protons.

Strongly Emissive and Photostable Four‐Coordinate Organoboron N,C Chelates and Their Use in Fluorescence Microscopy

Six strongly fluorescent four-coordinate organoboron N,C chelates containing an aryl isoquinoline skeleton were prepared. Remarkably, the fluorescence quantum yields reach values of up to 0.74 in oxygen-free toluene. The strong B-N interaction was corroborated by the single-crystal X-ray analysis of two dyes. The intramolecular charge-transfer character of the fluorophores was evidenced by solvatochromism studies and time-dependent DFT calculations at the PCM(toluene)/CAM-B3LYP/6-311++G(2d,p)//PCM(toluene)/B3LYP/6-311G(2d,p) level of theory. The compounds combine high chemical stability with high photostability, especially when equipped with electron-donating substituents. The strong fluorescence and the large Stokes shifts predestine these compounds for use in confocal fluorescence microscopy. This was demonstrated for the imaging of the N13 mouse microglial cell line. Moreover, significant two-photon absorption cross sections (up to 61 GM) allow the use of excitation wavelengths in the near-infrared region (>800 nm).

Organic Fluorescent Thermometers Based on Borylated Arylisoquinoline Dyes

Borylated arylisoquinolines with redshifted internal charge-transfer (ICT) emission were prepared and characterized. Upon heating, significant fluorescence quenching was observed, which forms the basis for a molecular thermometer. In the investigated temperature range (283-323 K) an average sensitivity of -1.2 to -1.8% K(-1) was found for the variations in fluorescence quantum yield and lifetime. In the physiological temperature window (298-318 K) the average sensitivity even reaches values of up to -2.4% K(-1). The thermometer function is interpreted as the interplay between excited ICT states of different geometry. In addition, the formation of an intramolecular Lewis pair can be followed by (11)B NMR spectroscopy. This provides a handle to monitor temperature-dependent ground-state geometry changes of the dyes. The role of steric hindrance is addressed by the inclusion of a derivative that lacks the Lewis pair formation.

Preparation and pH-switching of fluorescent borylated arylisoquinolines for multilevel molecular logic.

The preparation of pH-switchable fluorescent borylated arylisoquinoline dyes via a flexible iridium-catalyzed route is reported. The obtained dyes feature aromatic amino substitution and lateral aliphatic amino groups as electron donors. The photophysical properties of the internal charge transfer dyes were studied, which was complemented by density functional theory calculations. Appreciable fluorescence quantum yields (Φf up to ca. 0.4) and characteristic spectral fingerprints in the green to red emission range were observed. The fluorescence modulation upon multiple and orthogonal protonation with triflic acid was studied and led to the interpretation of multilevel switching including off-on-off, ternary, and quaternary responses.

Borylated Arylisoquinolines: Photophysical Properties and Switching Behavior of Promising Tunable Fluorophores

A series of nine borylated arylisoquinolines has been prepared with systematic variation in their electronic properties and their photophysical properties were investigated. The color of their fluorescence can be finely tuned by changing the properties of the aryl moiety, which is involved in internal-charge-transfer processes. For example, methoxy-substituted compound 5 showed an intense green emission, whereas dimethylamino-substituted compound 6 showed an orange-red emission. These new fluorophores were tested for their potential as molecular switches with external ionic stimuli, such as protons and fluoride ions. On the one hand, protonation of the isoquinoline moiety led to fluorescence enhancement for compounds that showed weak charge transfer and fluorescence quenching for compounds that showed strong charge transfer. On the other hand, the formation of ate complexes with fluoride led to strong fluorescence quenching in all of the investigated cases.

Electronic and Functional Scope of Boronic Acid Derived Salicylidenehydrazone (BASHY) Complexes as Fluorescent Dyes

A series of boronic acid derived salicylidenehydrazone (BASHY) complexes was prepared and photophysically characterized. The dye platform can be modified by (a) electronic tuning along the cyanine-type axis via modification of the donor-acceptor pair and (b) functional tuning via the boronic acid residue. On the one hand, approach (a) allows the control of photophysical parameters such as Stokes shift, emission color, and two-photon-absorption (2PA) cross section. The resulting dyes show emission light-up behavior in nonpolar media and are characterized by high fluorescence quantum yields (ca. 0.5-0.7) and brightness (ca. 35000-40000 M-1 cm-1). Moreover, the 2PA cross sections reach values in the order of 200-300 GM. On the other hand, the variation of the dye structure through the boronic acid derived moiety (approach (b)) enables the functionalization of the BASHY platform for a broad spectrum of potential applications, ranging from biorelevant contexts to optoelectronic materials. Importantly, this functionalization is generally electronically orthogonal with respect to the dyes photophysical properties, which are only determined by the electronic structure of the cyanine-type backbone (approach (a)). Rare exceptions to this generalization are the presence of redox-active residues (such a triphenylamine or pyrene). Finally, the advantageous photophysics is complemented by a significant photostability.

Supramolecular control of phthalocyanine dye aggregation

A phthalocyaninato zinc(II) dye with four peripheral N-methylpyridinium anchor groups and its higher-order complex with cucurbit[7]uril were photophysically characterised. The supramolecular host–guest interaction with the anchor yielded a deaggregation of the dye in neutral water solutions. This was signalised by the formation of a sharp UV–vis absorption band at ca. 690 nm and a dramatic increase in the fluorescence. While the aggregated dye is essentially non-fluorescent (Φf < 2 × 10− 3), the supramolecular complex with cucurbit[7]uril shows an emission quantum yield of Φf = 2.7 × 10− 2. The apparent 1:1 binding constant of each pyridinium anchor unit was determined as K = 7.4 × 104 M− 1. Competitors such as polyamines (e.g. spermine), and also metal cations, reverse the complexation. This can be followed by the decrease in the fluorescence signal and the disappearance of the characteristic UV–vis absorption signature of the deaggregated dye. The effect was used to investigate the binding of 11 metal cations (Li+, Na+, K+, Rb+, Cs+, Mg2+, Ca2+, Sr2+, Zn2+, Eu3+, Gd3+). Cations with multiple charges and a large ionic radius are found to form the strongest complexes with cucurbit[7]uril (K>1 × 103 M− 1 for Ca2+, Sr2+, Eu3+).