Photomechanochemistry: harnessing mechanical forces to enhance photochemical reactions

• Francesco Mele,
• Ana M. Constantin,
• Andrea Porcheddu,
• Raimondo Maggi,
• Giovanni Maestri,
• Nicola Della Ca’ and
• Luca Capaldo

Beilstein J. Org. Chem. 2025, 21, 458–472, doi:10.3762/bjoc.21.33

• surface area exposed to light but also to allow the motions within the crystal. In another instance, MacGillivray and colleagues reported the synthesis of rctt-tetrakis(4-pyridyl)cyclobutane (2.3) via [2 + 2] photodimerization of trans-1,2-bis(4-pyridyl)ethylene (2.1) via supramolecular catalysis by 4,6

• . Mechanochemically triggered pedal-like motion in solid-state [2 + 2] photochemical cycloaddition for the formation of cyclobutanes [62]. Mechanically promoted [2 + 2] photodimerization of trans-1,2-bis(4-pyridyl)ethylene (2.1) via supramolecular catalysis by 4,6-dichlororesorcinol (2.2) in the solid state [64

Beyond symmetric self-assembly and effective molarity: unlocking functional enzyme mimics with robust organic cages

• Keith G. Andrews

Beilstein J. Org. Chem. 2025, 21, 421–443, doi:10.3762/bjoc.21.30

• symmetry to enable promising catalytic modes. Keywords: cavity confinement catalysis; enzyme mimicry; robust organic cages; self-assembly; supramolecular catalysis; Introduction I frequently introduce my research on organic cage enzyme mimics with the following observation. For hundreds of years

• hydrophobic hosts [37]. Directed polarization, the basis for organocatalysis, is rare in cavity catalysis. Now, I believe the field of supramolecular catalysis to be on the cusp of putting these two elements – “organization and polarization” or “confinement and dual activation” – together with greater

• of control of rigidity in supramolecular catalysis [25]. In contrast to cage 2, cage 1 has access to at least 5 conformers by amide rotation, covering a flexibility of perhaps 1.5–2 Å (≈20% increase from the smallest size) [39][40]. This “macro-flexibility” is more akin to large enzyme-like movements

A fluorescent probe for detection of Hg²⁺ ions constructed by tetramethyl cucurbit[6]uril and 1,2-bis(4-pyridyl)ethene

• Xiaoqian Chen,
• Naqin Yang,
• Yue Ma,
• Xinan Yang and
• Peihua Ma

Beilstein J. Org. Chem. 2023, 19, 864–872, doi:10.3762/bjoc.19.63

• form various host–guest inclusion complexes [16][17][18][19][20], which have broad application prospects in supramolecular catalysis [21][22][23], molecular recognition [24][25], and drug delivery [26][27]. In recent years, in the field of supramolecular chemistry, the detection of analytes based on

Supramolecular approaches to mediate chemical reactivity

• Pablo Ballester,
• Qi-Qiang Wang and
• Carmine Gaeta

Beilstein J. Org. Chem. 2022, 18, 1463–1465, doi:10.3762/bjoc.18.152

• reactions by a biomimetic approach [3][4]. Very recently, many efforts have been devoted to study supramolecular catalysis processes [5][6][7][8][9][10][11][12][13][14] in which macrocyclic hosts, self-assembled capsules and metallo-cages were employed as catalysts or nanocontainers. The primary

• characteristic of supramolecular catalysis is that the general modes of activation based on intermolecular interactions can operate on substrates in a selective way, and in confined environment, like the active site of natural enzymes [5][6][7][8][9][10][11][12][13][14]. As a result, molecular recognition of the

• substrate(s) and potentially the transition state is essential in supramolecular catalysis. Supramolecular catalysis finds inspiration in natural enzymes, which show catalytic features such as substrates and products selectivity, efficiency, geometric control, and acceleration of chemical reactivity [1]. If

Heteroleptic metallosupramolecular aggregates/complexation for supramolecular catalysis

• Prodip Howlader and
• Michael Schmittel

Beilstein J. Org. Chem. 2022, 18, 597–630, doi:10.3762/bjoc.18.62

• Prodip Howlader Michael Schmittel Center of Micro- and Nanochemistry and (Bio)Technology, Universität Siegen, Organische Chemie I, Adolf-Reichwein-Str. 2, D-57068 Siegen, Germany 10.3762/bjoc.18.62 Abstract Supramolecular catalysis is reviewed with an eye on heteroleptic aggregates/complexation

• allows, as demonstrated by Nature by the multicomponent ATP synthase motor, a more detailed and refined configuration of purposeful machinery. Furthermore, (metallo)supramolecular catalysis is shown to extend beyond the single "supramolecular unit" and to reach far into the field and concepts of systems

• chemistry and information science. Keywords: heteroleptic complexation; information science; supramolecular catalysis; switching catalysis; systems chemistry; Introduction Supramolecular catalysis [1][2][3] for most chemists is associated with a catalytically active capsule providing either activating

Bioinspired tetraamino-bisthiourea chiral macrocycles in catalyzing decarboxylative Mannich reactions

• Hao Guo,
• Yu-Fei Ao,
• De-Xian Wang and
• Qi-Qiang Wang

Beilstein J. Org. Chem. 2022, 18, 486–496, doi:10.3762/bjoc.18.51

• Mannich reactions; supramolecular catalysis; thiourea; Introduction In the past decades, the development of supramolecular chemistry has enabled abundant host scaffolds and assembly tools for boosting catalytic processes, and stimulated the emergence of supramolecular catalysis [1][2][3][4][5][6][7][8][9

A resorcin[4]arene hexameric capsule as a supramolecular catalyst in elimination and isomerization reactions

• Tommaso Lorenzetto,
• Fabrizio Fabris and
• Alessandro Scarso

Beilstein J. Org. Chem. 2022, 18, 337–349, doi:10.3762/bjoc.18.38

• compared to many other strong Brønsted or Lewis acids. Keywords: cationic intermediates; encapsulation; organocatalysis; resorcin[4]arene hexamer; supramolecular catalysis; Introduction In enzymatic catalysis, the substrate is selected matching the size, shape and specific functional groups present in

• states of the reaction with impressive accelerations, substrate, and product selectivities. The development of artificial catalytic systems able to activate substrates and to stabilize intermediate species through weak noncovalent interactions is the scope of supramolecular catalysis [1][2][3][4

• 16 represents a competitive catalytic system especially considering the milder experimental conditions, the lack of strong Brønsted or Lewis acids and the simple supramolecular catalytic approach. Conclusion In conclusion, we described a series of examples of supramolecular catalysis where the

A Se···O bonding catalysis approach to the synthesis of calix[4]pyrroles

• Qingzhe Tong,
• Zhiguo Zhao and
• Yao Wang

Beilstein J. Org. Chem. 2022, 18, 325–330, doi:10.3762/bjoc.18.36

• . Keywords: calix[4]pyrrole; chalcogen bonding; ketones; Se···O bonding interactions; supramolecular catalysis; Introduction Noncovalent catalysis has been established as one of the fundamental concepts in organic synthesis that enables achieving numerous chemical transformations [1]. Among these

A chiral self-sorting photoresponsive coordination cage based on overcrowded alkenes

• Constantin Stuckhardt,
• Diederik Roke,
• Wojciech Danowski,
• Edwin Otten,
• Sander J. Wezenberg and
• Ben L. Feringa

Beilstein J. Org. Chem. 2019, 15, 2767–2773, doi:10.3762/bjoc.15.268

• coordination complexes (SCCs) represent a promising class of compounds which have been used in a variety of molecular systems [1][2][3][4][5][6]. Taking advantage of the vacant cavity inside these complexes, SCCs have been applied in drug delivery [6][7][8], supramolecular catalysis [9][10][11][12], X-ray

1,2,3-Triazolium macrocycles in supramolecular chemistry

• Mastaneh Safarnejad Shad,
• Pulikkal Veettil Santhini and
• Wim Dehaen

Beilstein J. Org. Chem. 2019, 15, 2142–2155, doi:10.3762/bjoc.15.211

• have led to applications in molecular recognition, sensing, molecular machines and devices, supramolecular polymers, stimuli-responsive materials, supramolecular catalysis and drug-delivery systems [4][5][6][7]. Inspired by the attractive role of various N-heterocyclic building blocks such as

Synthesis and anion binding properties of phthalimide-containing corona[6]arenes

• Meng-Di Gu,
• Yao Lu and
• Mei-Xiang Wang

Beilstein J. Org. Chem. 2019, 15, 1976–1983, doi:10.3762/bjoc.15.193

• [1][2][11][12]. Moreover, the designed macrocycles are useful molecular tools in the investigation of supramolecular catalysis and reaction mechanisms [1][2][13][14][15][16]. Heteracalixaromatics or heteroatom-bridged calix(het)arenes [17][18][19][20][21] are synthetic macrocycles composed of

Novel macrocycles – and old ones doing new tricks

• Wei Jiang and
• Christoph A. Schalley

Beilstein J. Org. Chem. 2019, 15, 1838–1839, doi:10.3762/bjoc.15.178

• diversified. They are not only tools for studying molecular recognition and molecular machines, but are also key components for sensing, supramolecular catalysis, (chiral) separation, drug delivery, or smart materials. Many new macrocycles have recently been reported, with pillararenes being one of the most

Fabrication, characterization and adsorption properties of cucurbit[7]uril-functionalized polycaprolactone electrospun nanofibrous membranes

• Changzhong Chen,
• Fengbo Liu,
• Xiongzhi Zhang,
• Zhiyong Zhao and
• Simin Liu

Beilstein J. Org. Chem. 2019, 15, 992–999, doi:10.3762/bjoc.15.97

• ][23][24]. Through hydrophobic effects, ion–dipole interactions, and/or hydrogen bonding, CB[n]s show selective molecular recognition properties towards cationic and neutral guests [25][26]. In the last two decades, CB[n]s have been used for a variety of applications including supramolecular catalysis

Mechanochemistry of supramolecules

• Anima Bose and
• Prasenjit Mal

Beilstein J. Org. Chem. 2019, 15, 881–900, doi:10.3762/bjoc.15.86

• ]. Supramolecular catalysis The concept of supramolecular catalysis mainly is based on the use of supramolecular chemistry, molecular recognition, host–guest chemistry, etc. for catalysis [96]. The field originated with the understanding of enzymatic system which is conceptually different from traditional organic

• , supramolecular catalysis proposes a much simpler model to understand the catalytic activity of enzymes. In 2010, MacGillivray and co-workers have demonstrated the concept of “supramolecular catalysis” in a hydrogen-bond-assisted self-assembled formation of a [2 + 2]-cycloaddition product. The reaction was found

• ]-cycloaddition methodology. They used the vertex grinding technique where solid-state grinding and UV irradiation was done simultaneously [111] and verified co-crystal formation of a resorcinol derivative with dipyridylethylene in the solid state. Also, the supramolecular catalysis of [2 + 2] photodimerization

Asymmetric Michael addition reactions catalyzed by calix[4]thiourea cyclohexanediamine derivatives

• Zheng-Yi Li,
• Hong-Xiao Tong,
• Yuan Chen,
• Hong-Kui Su,
• Tangxin Xiao,
• Xiao-Qiang Sun and
• Leyong Wang

Beilstein J. Org. Chem. 2018, 14, 1901–1907, doi:10.3762/bjoc.14.164

• and yields of the Michael reactions. Supramolecular catalysis has drawn tremendous interest in the past few years [15][16][17][18][19][20][21][22][23]. In this context, calixarenes are ideal supramolecular macrocyclic scaffolds for the design of molecular receptors and organocatalysts due to their

Superstructures with cyclodextrins: Chemistry and applications IV

• Gerhard Wenz

Beilstein J. Org. Chem. 2017, 13, 2157–2159, doi:10.3762/bjoc.13.215

• magnetic resonance imaging (MRI) [22]. Well-defined fluorescent polyrotaxanes with alternating, threaded cucurbit[6]uril and CD rings were assembled by Fraser Stoddart’s group via an alkyne–azide click reaction exploiting supramolecular catalysis [23][24]. The concurrent radical copolymerization of 1,3

Topochemical control of the photodimerization of aromatic compounds by γ-cyclodextrin thioethers in aqueous solution

• Hai Ming Wang and
• Gerhard Wenz

Beilstein J. Org. Chem. 2013, 9, 1858–1866, doi:10.3762/bjoc.9.217

• photoproduct from aqueous solution by liquid/liquid extraction simplifies the scale up. Yields of photodimer based on the complex were nearly quantitative. The observed supramolecular catalysis was explained by the high pre-organization resulting from the tight packing of the two guests in the cavity, which