Boosting the Host–Guest Binding by Programming the Curvature in Geodesic Nanoribbons

JACS Au, Journal Year: 2025, Volume and Issue: unknown

Published: March 13, 2025

Language: Английский

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Biomimetic Parallel Vein-like Two-Dimensional Supramolecular Layers Containing Embedded One-Dimensional Conduits Driven by Cation−π Interaction and Hydrogen Bonding to Promote Photocatalytic Hydrogen Evolution

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: April 8, 2025

Two-dimensional supramolecular assemblies (2DSAs) with well-defined nanostructures have emerged as promising candidates for diverse applications, particularly in photocatalysis. However, it still remains a significant challenge to simultaneously achieve effective electron transport and multiple active sites 2DSA, even though this is crucial enhancing photocatalytic performance. This reason can be attributed the lack of suitable structural paradigm that enables both intermolecular orbital overlap increased substrate contact. Inspired by parallel venation monocotyledons facilitate transfer, we overcome limitation, study, integrating parallel-arranged one-dimensional (1D) conduits edge-on packing motifs construct biomimetic, vein-like two-dimensional layers (PV-2DSLs) through hierarchical self-assembly cationically modified, rigid multiarmed monomers. The resulting PV-2DSLs exhibit long-range aromatic cation-π stacking transport. Importantly, unique feature these orderly embedding 1D within 2D plane, which significantly different from conventional channels formed vertical porous materials. These promote multielectron transfer pathways, leading enhanced charge separation carrier when coupled stacking. As consequence, long excited state lifetime, improved hydrogen production rates up 3.5 mmol g-1 h-1, approximately 17.5 times higher than counterpart without (0.2 h-1).

Language: Английский

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Polymorphism and flexibility of six-porphyrin nanorings in the solid state

Published: Aug. 16, 2024

Butadiyne-linked porphyrin nanorings are fascinating nanometer-sized platforms for exploring electronic delocalization and aromaticity, they mimic ultra-fast photosynthetic energy-transfer phenomena in plants purple bacteria. However, little is known about how interact the solid state. Here, we compare crystal structures of several polymorphs a six-porphyrin nanoring template complex, report structure free-base co-crystallized with C60. The differ not only molecular packing; also feature different conformations. slightly too small cavity nanoring, this size mismatch can be accommodated by two types distortion: either zinc atoms pulled away from planes porphyrins, or contract adopting ruffled conformation, butadiyne links alternatingly above below plane six centers. template-bound ring forms sheets tubular stacks interdigitated aryl groups. Upon demetallation, becomes more flexible, highly elliptical conformation on co-crystallization features infinite solvent filled channels channel diameter 13.5 Å. high porosity these materials points towards possible applications as porous light- harvesting frameworks.

Language: Английский

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Polymorphism and flexibility of six-porphyrin nanorings in the solid state

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

The template complex of a zinc porphyrin nanoring forms several pseudopolymorphs featuring different conformations the π-system. metal-free is even more flexible, and adopts an elliptical geometry when co-crystallized with C 60 .

Language: Английский

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Pentacosacyclenes: Cruciform Molecular Nanocarbons Based on Cyclooctatetraene

Chemical Science, Journal Year: 2024, Volume and Issue: unknown

Published: Jan. 1, 2024

Pentacosacyclene (PC) and pentacosacyclene tetraimide (PCTI) were obtained in concise syntheses involving radial extension of tridecacyclene. PC is an electron-rich hydrocarbon with a C

Language: Английский

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