György Szalóki

A simple molecule-based octastate switch.

Dithienylethene oxazolidine hybrid system connected through an isomerizable double bond exists under eight molecular states on demand. Combinations of electrocyclization of dithienylethene, Z/E isomerization and acid-base oxazolidine change cause selective addressabilities. Two intricate gated photochromic performances allow the execution of an 8-step molecular switch, which renders this molecular system the most complex known up to date.

Reversible Guest Uptake/Release by Redox-Controlled Assembly/Disassembly of a Coordination Cage

Controlling the guest expulsion process from a receptor is of critical importance in various fields. Several coordination cages have been recently designed for this purpose, based on various types of stimuli to induce the guest release. Herein, we report the first example of a redox-triggered process from a coordination cage. The latter integrates a cavity, the panels of which are based on the extended tetrathiafulvalene unit (exTTF). The unique combination of electronic and conformational features of this framework (i.e. high π-donating properties and drastic conformational changes upon oxidation) allows the reversible disassembly/reassembly of the redox-active cavity upon chemical oxidation/reduction, respectively. This cage is able to bind the three-dimensional B12 F12 (2-) anion in a 1:2 host/guest stoichiometry. The reversible redox-triggered disassembly of the cage could also be demonstrated in the case of the host-guest complex, offering a new option for guest-delivering control.

Indolinooxazolidine: a versatile switchable unit.

The design of multiresponsive systems continues to arouse a lot of interest. In such multistate/multifunctional systems, it is possible to isomerize a molecular system from one metastable state to another by application of different stimulation such as light, heat, proton, or electron. In this context, some researches deal with the design of multimode switch where a same interconversion between two states could be induced by using indifferently two or more different kind of stimuli. Herein, we demonstrate that the association of an indolinooxazolidine moiety with a bithiophene unit allows the development of a new trimode switch. A reversible conversion between a colorless closed form and a colorful open form can be equally performed by light, proton, or electrical stimulation. In addition, the oxidation of this system allows the generation of a third metastable state.

Huge electro-/photo-/acidoinduced second-order nonlinear contrasts from multiaddressable indolinooxazolodine.

In this work, linear and nonlinear optical properties of electro-/acido-/photoswitchable indolino[2,1-b]oxazolidine derivatives were investigated. The linear optical properties of the closed and open forms have been characterized by UV-visible and IR spectroscopies associated with DFT calculations. Nonlinear optical properties of the compounds have been obtained by ex situ and in situ hyper-Rayleigh experiments in solution. We show that protonated, oxidized, and irradiated open forms exhibit the same visible absorption and NLO features. In particular, the closed and open forms exhibit a huge contrast of the first hyperpolarizability with an enhancement factor of 40-45. Additionally, we have designed an original electrochemical cell that allows to monitor in situ the hyper-Rayleigh response upon electrical stimulus. We report notably a partial but good and reversible NLO contrast in situ during oxidation/reduction cycles. Thereby, indolinooxazolidine moieties are versatile trimodal switchable units which are very promising for applications in devices.

Controlling the Host‐Guest Interaction Mode through a Redox Stimulus

A proof-of-concept related to the redox-control of the binding/releasing process in a host-guest system is achieved by designing a neutral and robust Pt-based redox-active metallacage involving two extended-tetrathiafulvalene (exTTF) ligands. When neutral, the cage is able to bind a planar polyaromatic guest (coronene). Remarkably, the chemical or electrochemical oxidation of the host-guest complex leads to the reversible expulsion of the guest outside the cavity, which is assigned to a drastic change of the host-guest interaction mode, illustrating the key role of counteranions along the exchange process. The reversible process is supported by various experimental data (1 H NMR spectroscopy, ESI-FTICR, and spectroelectrochemistry) as well as by in-depth theoretical calculations performed at the density functional theory (DFT) level.

Reversible C60 Ejection from a Metallocage through the Redox-Dependent Binding of a Competitive Guest

The reversible encapsulation of a tetrapyridyl extended-tetrathiafulvalene (exTTF)-based ligand (m-Py)exTTF by a tetragonal Zn-porphyrin-based prismatic nanocage (1) is described. The reversible uptake and release of the (m-Py)exTTF guest proceeds through drastic electronic and conformational changes occurring upon oxidation of the latter. This reversible system has been explored in a guest-exchange process, by addition of (m-Py)exTTF to the host-guest complex [C60 ⊂1], leading to fullerene C60 ejection from the host cavity. Remarkably, the subsequent redox-triggered ejection of (m-Py)exTTF, leads to the recovery of the empty cage 1, which remains available for further C60 encapsulation. The C60 ejection is justified by the preferable coordination of the pyridine anchors of (m-Py)exTTF to the two Zn-porphyrin units of 1. This approach, based on the use of a switchable competitive guest, offers a promising new strategy for guest-delivery control.

Indolino-oxazolidine Acido and Photochromic System investigated by NMR and DFT Calculations

Three addressable indolino-oxazolidine units connected through an isomerizable double bond to a substituted thiophene represent a smart example of a multiaddressable system whose reversible responses could be selectively activated on demand. Experimental and theoretical approaches to push forward the understanding of the system mechanism and set pathways to design optimized compounds for suitable application are here presented. NMR and UV-visible spectroscopies are used for structural and kinetic studies, while density functional theory (DFT) calculations pave the way to highlight energetic and electronic processes that are involved. Substitution and solvent effects toward the reactivity of the compounds are experimentally studied and combined with theoretical calculations. The most efficient and selective stimuli to travel between the four possible states resulting from the ring-opening of indolino[2,1- b]oxazolidine (generally referenced as BOX) derivatives and the trans-cis isomerization of the ethylenic junction are elucidated.

Redox-Driven Transformation of a Discrete Molecular Cage into an Infinite 3D Coordination Polymer

Two M12 L6 redox-active self-assembled cages constructed from an electron-rich ligand based on the extended tetrathiafulvalene framework (exTTF) and metal complexes with a linear geometry (PdII and AgI ) are depicted. Remarkably, based on a combination of specific structural and electronic features, the polycationic self-assembled AgI coordination cage undergoes a supramolecular transformation upon oxidation into a three-dimensional coordination polymer, that is characterized by X-ray crystallography. This redox-controlled change of the molecular organization results from the drastic conformational modifications accompanying oxidation of the exTTF moiety.

Properties and Applications of Indolinooxazolidines as Photo-, Electro-, and Acidochromic Units

The aim of this chapter was to introduce the readers to indolinooxazolidines (IndOxa), a new family of molecular switches. First, in a short historical account their evolution is followed from their first appearance in the 1970s until today. The second section concentrates on the general structural features of the indolinooxazolidine motif, which are closely related to those of the spiropyrans. In the core of their chemistry lies the oxazolidine ring opening that is discussed in the following. Owing to the facility of the very same ring opening, they show chromophoric properties and can be addressed using different stimuli, such as light irradiation, change in electrical potential and pH. For this reason, the last three sections are devoted to provide a general understanding on their photo-, electro-, and acidochromic properties.