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  1. Bridging the current gap between the precision and efficiency demonstrated by natural systems and synthetic materials requires interfacing and independently controlling multiple stimuli-responsive building blocks in a single platform. The mentioned orthogonal control over material properties (i.e., the ability to selectively activate one stimuli-responsive moiety without affecting another) could pave the way for a multitude of applications, including logic-gated optoelectronics, on-demand drug delivery platforms, and molecular shuttles, for example. In this Review, we highlight the recent successful strategies to achieve orthogonal control over material properties using a combination of stimuli-responsive building blocks and multiple independent stimuli. We begin by surveying the fundamental studies of multi-stimuli-responsive systems, which utilize a variety of stimuli to activate a single stimuli-responsive moiety (e.g., spiropyran, diarylethene, or dihydroazulene derivatives), because these studies lay the foundation for the design of systems containing more than one independently controlled fragment. As a next step, we overview the emerging field focusing on systems which are composed of more than one unique stimuli-responsive unit that can respond to independent stimuli, including distinct excitation wavelengths, or a combination of light, heat, pH, potential, or ionic strength. Recent advances clearly demonstrate how strategic coupling of orthogonally controlled stimuli-responsive units can allow for selective modulation of a range of material properties, such as conductivity, catalytic performance, and biological activity. Thus, the highlighted studies foreshadow the emerging role of materials with orthogonally controlled properties to impact the next generation of photopharmacology, nanotechnology, optoelectronics, and biomimetics.

     
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    Free, publicly-accessible full text available March 1, 2025
  2. Free, publicly-accessible full text available August 22, 2024
  3. Abstract

    The forthcoming generation of materials, including artificial muscles, recyclable and healable systems, photochromic heterogeneous catalysts, or tailorable supercapacitors, relies on the fundamental concept of rapid switching between two or more discrete forms in the solid state. Herein, we report a breakthrough in the “speed limit” of photochromic molecules on the example of sterically-demanding spiropyran derivatives through their integration within solvent-free confined space, allowing for engineering of the photoresponsive moiety environment and tailoring their photoisomerization rates. The presented conceptual approach realized through construction of the spiropyran environment results in ~1000 times switching enhancement even in the solid state compared to its behavior in solution, setting a record in the field of photochromic compounds. Moreover, integration of two distinct photochromic moieties in the same framework provided access to a dynamic range of rates as well as complementary switching in the material’s optical profile, uncovering a previously inaccessible pathway for interstate rapid photoisomerization.

     
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  4. In this Feature Article, we survey the advances made in the field of fulleretic materials over the last five years. Merging the intriguing characteristics of fulleretic molecules with hierarchical materials can lead to enhanced properties of the latter for applications in optoelectronic, biomaterial, and heterogeneous catalysis sectors. As there has been significant growth in the development of fullerene- and corannulene-containing materials, this article will focus on studies performed during the last five years exclusively, and highlight the recent trends in designing fulleretic compounds and understanding their properties, that has enriched the repertoire of carbon-rich functional materials. 
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  5. Abstract

    Die Fortschritte, die in den letzten fünf Jahren auf dem Gebiet der Stimuli‐reaktiven Katalyse erzielt wurden, mit dem Schwerpunkt auf neuen, kürzlich erschienenen Richtungen und Anwendungen, werden dargestellt. Diskutiert werden metallfreie Katalysatoren und metallorganische Komplexe sowie biomimetische Systeme und erweiterte Strukturen, die eine schaltbare katalytische Reaktivität für eine Vielzahl von organischen Reaktionen aufweisen. Lichtaktivierte Systeme, die aus photochromen Molekülen bestehen, welche in der Lage sind, Reaktionsgeschwindigkeit, Ausbeute oder Enantioselektivität auf Grundlage der geometrischen und elektronischen Veränderungen im Zusammenhang mit der Photoisomerisierung zu modulieren, stehen im Mittelpunkt der ausführlichen Diskussion. Alternative Stimuli wie pH‐Wert und Temperatur, die entweder allein oder in Kombination mit Licht angewendet werden können, werden ebenfalls behandelt. Die jüngsten Fortschritte zeigen deutlich, dass die Möglichkeit, das Verhalten eines Katalysators durch einen externen Stimulus fein abzustimmen, ein leistungsfähiges Instrument ist, das die Landschaft der nachhaltigen Chemie verändern könnte.

     
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  6. Abstract

    The advances made in the field of stimuli‐responsive catalysis during the last five years with a focus on the novel recently‐emerged directions and applications have been surveyed. Metal‐free catalysts and organometallic complexes, as well as biomimetic systems and extended structures, which display switchable catalytic activity for a variety of organic transformations, are discussed. Light‐activated systems comprised of photochromic molecules capable of modulating reaction rate, yield, or enantioselectivity based on geometric and electronic changes associated with photoisomerization are the focus of the detailed discussion. Alternative stimuli, including pH and temperature, which could be applied either alone or in combination with light, are also addressed. Recent advances clearly demonstrate that the capability to finely tune catalyst behavior via an external stimulus is a powerful tool that could alter the landscape of sustainable chemistry.

     
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    Unprecedented one-step CC bond cleavage leading to opening of the buckybowl (π-bowl), that could provide access to carbon-rich structures with previously inaccessible topologies, is reported; highlighting the possibility to implement drastically different synthetic routes to π-bowls in contrast to conventional ones applied for polycyclic aromatic hydrocarbons. Through theoretical modeling, we evaluated the mechanistic pathways feasible for π-bowl planarization and factors that could affect such a transformation including strain and released energies. Through employment of Marcus theory, optical spectroscopy, and crystallographic analysis, we estimated the possibility of charge transfer and electron coupling between “open” corannulene and a strong electron acceptor such as 7,7,8,8-tetracyanoquinodimethane. Alternative to a one-pot solid-state corannulene “unzipping” route, we reported a nine-step solution-based approach for preparation of novel planar “open” corannulene-based derivatives in which electronic structures and photophysical profiles were estimated through the energies and isosurfaces of the frontier natural transition orbitals. 
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