Tripodal Triptycenes as a Versatile Building Block for Highly Ordered Molecular Films and Self-Assembled Monolayers

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 7, 2025

ConspectusThe design of properties and functions molecular assemblies requires not only a proper choice building blocks but also control over their packing arrangements. A highly versatile unit in this context is particular type triptycene with substituents at the 1,8,13-positions, called tripodal triptycene, which offers predictable multiple functionalization sites, both opposite 4,5,16- or 10 (bridgehead)-positions. These are capable two-dimensional (2D) nested hexagonal packing, leading to formation 2D sheets, undergo one-dimensional (1D) stacking into well-defined "2D+1D" structures. This ability makes it possible form large-area films having long-range structural integrity even on polymer substrates, can be used enhance performance organic devices. Importantly, assembly triptycenes robust impaired when chemically modified functional units chains. In addition, introducing suitable functionalities that act as anchoring groups results reliable monomolecular application-relevant inorganic generally considered quite challenging task. Self-assembled monolayers (SAMs) have been formed Au(111), Ag(111), indium tin oxide. On gold, these SAMs feature typical whereas, silver, distinct polymorphism several different motifs occurs. Along basic, nonsubstituted SAMs, specifically functionalized designed. substitution pattern three nitrile tail build outermost surface triptycene-based SAM has allowed for study femtosecond charge transfer dynamics across framework, emphasis so-called matrix effects involving intramolecular pathways. The bridgehead position ferrocene group enabled single-molecule observation redox reactions creation unique rectifiers, exhibiting effective rectification very low bias voltage. Complementary synthesis complex triptycenes, strategy on-surface click Indeed, an ethynyl 10-position, azide functionalities, works well, allowing successive layer deposition. tested electron beam lithography (EBL) nanofabrication, finding serve negative resists EBL due efficient cross-linking, giving rise triptycene-stemming carbon nanomembranes (CNM). membranes lowest lateral material densities date CNM preparation, them regard.

Language: Английский

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

Beilstein Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 21, P. 421 - 443

Published: Feb. 24, 2025

The bespoke environments in enzyme active sites can selectively accelerate chemical reactions by as much 1019. Macromolecular and supramolecular chemists have been inspired to understand mimic these accelerations selectivities for applications catalysis sustainable synthesis. Over the past 60+ years, mimicry strategies evolved with changing interests, understanding, synthetic advances but, ubiquitously, research has focused on use of a molecular "cavity". activities different cavities vary subset features available particular cavity type. Unsurprisingly, without access mimics able encompass more/all functional sites, examples cavity-catalyzed processes demonstrating enzyme-like rate remain rare. This perspective will briefly highlight some key traditional catalysis, type, order contextualize recent development robust organic cage catalysts, which exploit stability, functionality, reduced symmetry enable promising catalytic modes.

Language: Английский

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Triptycepenes: Synthesis, Metal Complexes, and Their Reactivity in Catalytic Reactions

Organometallics, Journal Year: 2025, Volume and Issue: unknown

Published: May 29, 2025

Language: Английский

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1,4,5,8-tetrasubstituted dihydroanthracene-based triptycene trisquinones: Synthesis, structural, and physicochemical characterization

Synthetic Communications, Journal Year: 2024, Volume and Issue: 54(15), P. 1263 - 1272

Published: July 25, 2024

1,4,5,8-tetrasubstituted dihyroanthracene-based triptycene trisquinones (TT) molecules, THAO-TT and tris(THAO)-TT, were synthesized by Diels–Alder reaction between TT 1,4,5,8-tetrakis(hexyloxy)anthracene to produce the extended derivatives containing electron-accepting functionality. The prepared THOA-TT tris(THOA)-TT exhibited excellent thermal stability owing rigid framework. optical redox properties of controlled homoconjugation benzoquinone units peripheral through connecting methine groups.

Language: Английский

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