Large‐Scale Synthesis of Helicene‐Like Molecules for the Design of Enantiopure Thin Films with Strong Chiroptical Activity

Helicenes are fascinating molecules owing to their unusual properties and applications in many fields from catalysis to organic electronics. Herein, we report a straightforward pathway for the synthesis of helicene‐like molecules on a gram scale in an enantiopure form. Thin‐film materials with good propagating optical properties and very high chiroptical responses have been grown by using pulsed laser ablation without altering the structure or the enantiopurity of the molecules. Moreover, electronic and vibrational circular dichroism spectroscopies coupled with theoretical calculations enabled some dependences of the chiroptical properties with the structure to be highlighted, for example, effects of rigidification, aromatization, or the state of matter (liquid versus solid).     

Complex Classical Fields: A Framework for Reflection Positivity

We explore a framework for complex classical fields, appropriate for describing quantum field theories. Our fields are linear transformations on a Hilbert space, so they are more general than random variables for a probability measure. Our method generalizes Osterwalder and Schrader’s construction of Euclidean fields. We allow complex-valued classical fields in the case of quantum field theories that describe neutral particles. From an analytic point-of-view, the key to using our method is reflection positivity. We investigate conditions on the Fourier representation of the fields to ensure that reflection positivity holds. We also show how reflection positivity is preserved by various spacetime compactifications of ${\mathbb{R}^{d}}$ in different coordinate directions.     

Transients and Evolution in NiTi

Many of the applications that seek to utilize shape memory alloys for their unique set of properties inevitably must deal, on some level, with the dimensional instability that is inherent to these materials under cyclic thermomechanical loading conditions. As a result, a better understanding of the transient and evolutionary behavior of a shape memory alloy is critical to both the successful design of useful actuation systems and development of accurate material models that can adequately capture the types of dimensional instability that can arise during component design. To this end, a set of experiments were conducted wherein the temperature cycling excursion was held fixed while the applied stress was varied. The results indicated that the extent of strain evolution produced under the initially applied stress has a significant impact on both the amount of transient that is observed as well as the rate of evolution observed under subsequent stress levels. In particular, lowering the applied stress to 50 MPa after cycling under an initial stress of 75 MPa did not stabilize the strain. However, lowering the applied stress to 50 MPa after cycling under an initial stress of 150 MPa produced a nearly saturated strain/temperature response. The thermomechanical observations are discussed in terms of the nature of strain evolution and its connection to the concept of a local/global minimization of the energy of the system, however, the exact mechanisms associated with these strain evolutions were not determined.     

Acid/Base‐Triggered Switching of Circularly Polarized Luminescence and Electronic Circular Dichroism in Organic and Organometallic Helicenes

Electronic circular dichroism and circularly polarized luminescence acid/base switching activity has been demonstrated in helicene‐bipyridine proligand 1 a and in its “rollover” cycloplatinated derivative 2 a . Whereas proligand 1 a displays a strong bathochromic shift (>160 nm) of the nonpolarized and circularly polarized luminescence upon protonation, complex 2 a displays slightly stronger emission. This strikingly different behavior between singlet emission in the organic helicene and triplet emission in the organometallic derivative has been rationalized by using quantum‐chemical calculations. The very large bathochromic shift of the emission observed upon protonation of azahelicene‐bipyridine 1 a has been attributed to the decrease in aromaticity (promoting a charge‐transfer‐type transition rather than a π–π* transition) as well as an increase in the HOMO–LUMO character of the transition and stabilization of the LUMO level upon protonation.     

Bridged to Fused Ring Interchange. Methodology for the Construction of Fused Cycloheptanes and Cyclooctanes. Total Syntheses of Ledol, Ledene, and Compressanolide

The type two intramolecular Diels-Alder reaction (T2IMDA) is an efficient method for the formation of medium rings. The methodology is particularly effective for the construction of seven- and eight-membered rings. A strategy for the synthesis of functionalized cycloheptanes and cyclooctanes has been developed that involves a bridged to fused ring interchange. The T2IMDA provides a synthesis for rigid bridged bicyclic molecules that can be stereoselectively elaborated before ozonolysis of the bridgehead double bond. Following oxidative cleavage, aldol condensation provides fused bicyclic ring systems that otherwise are difficult to synthesize. This methodology is amenable to the synthesis of terpene natural products. This is demonstrated here through total syntheses of (+/-)-ledol and (+/-)-ledene and a formal synthesis of (+/-)-compressanolide.