A High-Yielding Active Template Click Reaction (AT-CuAAC) for the Synthesis of Mechanically Interlocked Nanohoops.

Mechanically interlocked molecules (MIMs) represent an exciting yet underexplored area of research in the context of carbon nanoscience. Recently, work from our group and others has shown that small carbon nanotube fragments-[n]cycloparaphenylenes ([n]CPPs) and related nanohoop macrocycles-may be integrated into mechanically interlocked architectures by leveraging supramolecular interactions, covalent tethers, or metal-ion templates. Still, available synthetic methods are typically difficult and low yielding, and general methods that allow for the creation of a wide variety of these structures are limited. Here we report an efficient route to interlocked nanohoop structures via the active template Cu-catalyzed azide-alkyne cycloaddition (AT-CuAAC) reaction. With the appropriate choice of substituents, a macrocyclic precursor to 2,2'-bipyridyl embedded [9]CPP (bipy[9]CPP) participates in the AT-CuAAC reaction to provide [2]rotaxanes in near-quantitative yield, which can then be converted into the fully π-conjugated catenane structures. Through this approach, two nanohoop[2]catenanes are synthesized which consist of a bipy[9]CPP catenated with either Tz[10]CPP or Tz[12]CPP (where Tz denotes a 1,2,3-triazole moiety replacing one phenylene ring in the [n]CPP backbone).

Experimental and theoretical elucidation of SPAAC kinetics for strained alkyne-containing cycloparaphenylenes.

Tuning strained alkyne reactivity via organic synthesis has evolved into a burgeoning field of study largely focused on cyclooctyne, wherein physical organic chemistry helps guide rational molecular design to produce molecules with intriguing properties. Concurrent research in the field of carbon nanomaterials has produced new types of strained alkyne macrocycles, such as cycloparaphenyleneacetylenes, that possess uniquely curved aromatic π systems but hover on the edge of stability. In 2018, we introduced a strained alkyne scaffold that marries the synthetic accessibility and stability of cyclooctyne with the curved π system of carbon nanomaterials. These molecules are strained alkyne-containing cycloparaphenylenes (or [n+1]CPPs), which have been shown to possess size-dependent reactivity as well as the classic characteristics of the unfunctionalized parent CPP, such as a tunable HOMO-LUMO gap and bright fluorescence for large sizes. Herein, we elaborate further on this scaffold, introducing two modifications to the original design and fully characterizing the kinetics of the strain-promoted azide-alkyne cycloaddition (SPAAC) for each [n+1]CPP with a model azide. Additionally, we explain how electronic (the incorporation of fluorine atoms) and strain (a meta linkage which heightens local strain at the alkyne) modulations affect SPAAC reactivity via the distortion-interaction computational model. Altogether, these results indicate that through a modular synthesis and rational chemical design, we have developed a new family of tunable and inherently fluorescent strained alkyne carbon nanomaterials.

Progress toward colorimetric and fluorescent detection of carbonyl sulfide.

We report here that a fluorescent benzobisimidazolium salt (TBBI) can be used for the fluorescent and colorimetric detection of carbonyl sulfide (COS) over related heterocumulenes including CO2 and CS2 in wet MeCN. The reaction between TBBI and COS in the presence of fluoride yields a highly fluorescent (λem = 354 nm) and colored product (λmax = 321, 621 nm), that is readily observed by the naked eye. We view these results as a first step toward developing activity-based probes for COS detection.

Thiol-Ene Modified Amorphous Carbon Substrates: Surface Patterning and Chemically Modified Electrode Preparation.

Amorphous carbon (aC) films are chemically stable under ambient conditions or when interfaced with aqueous solutions, making them a promising material for preparing biosensors and chemically modified electrodes. There are a number of wet chemical methods capable of tailoring the reactivity and wettability of aC films, but few of these chemistries are compatible with photopatterning. Here, we introduce a method to install thiol groups directly onto the surface of aC films. These terminal thiols are compatible with thiol-ene click reactions, which allowed us to rapidly functionalize and pattern the surface of the aC films. We thoroughly characterized the aC films and confirmed the installation of surface-bound thiols does not significantly oxidize the surface or change its topography. We also determined the conditions needed to selectively attach alkene-containing molecules to these films and show the reaction is proceeding through a thiol-mediated reaction. Lastly, we demonstrate the utility of our approach by photopatterning the aC films and preparing ferrocene-modified aC electrodes. The chemistry described here provides a rapid means of fabricating sensors and preparing photoaddressable arrays of (bio)molecules on stable carbon interfaces.