U-shaped bisporphyrin molecules are clipped around SWCNTs using ring-closing metathesis yielding rotaxane-type derivatives, in which porphyrins and SWCNTs are connected through mechanical links.

We describe the reversible dispersion of SWCNTs through cooperative encapsulation within H-bonded dinucleoside macrocycles.

We present an easy drop-casting based functionalization of MoS2-based photodetectors that results in an enhancement of the photoresponse of about four orders of magnitude, reaching responsivities up to 100 A·W -1 . The functionalization is technologically trivial, air-stable, fully reversible and reproducible, and opens the door to the combination of 2D-materials with molecular dyes for the development of high performance photodetectors.Among the novel two-dimensional (2D) materials, 1-8 transition metal dichalcogenides (TMDCs) [9][10][11][12] show particularly promising electronic and optoelectronic properties. 13 In particular, their intrinsic bandgap within the visible part of the spectrum, makes them highly interesting materials for optoelectronic applications.14 In fact, the presence of a bandgap has allowed for the construction of a wealth of prototype electronic devices based on TMDCs. [15][16][17][18][19][20][21][22][23][24] In the last years, there has been a significant effort to modulate the optical properties of TMDCs in order to optimize the performance of the corresponding devices. Most of the strategies investigated so far rely on physical methods, such as strain-engineering, 25,26 fieldeffect doping, 12,27 or artificial stacking of different 2D materials. 28,29 In comparison, the chemical modification of TMDCs is still rather underexplored, despite the appealing combination of low-cost and high degree of control offered by synthetic chemistry. Examples of doping of TMDCs through surface charge-transfer using metal atoms, 30 gases, 31 and a few organic molecules has already been demonstrated. 32,33 Responsivities of just a few A·W -1 have been reported for MoS2 photodetectors functionalized with a rhodamine dye, 34 a rather modest value for MoS2-based photodetectors. Among the readily available organic dyes, perylenediimides (PDIs) and porphyrins show remarkable optical properties, including large molar absorptivity -ca. 10 5 M −1 cm −1 for PDIs and 10 6 M −1 cm −1 for porphyrins-, and outstanding photostability under ambient conditions. These intrinsic properties have made them two of the most popular families of organic dyes, particularly in the frame of photovoltaics. [35][36][37][38][39][40][41][42][43][44] However, their use for the modulation of the optoelectronic properties of TMDC-based devices has not been yet described. Considering this, we decided to investigate the effects of the noncovalent functionalization of MoS2 This is the post-peer reviewed version of the following article: A.J. Molina-Mendoza et al. "Engineering the optoelectronic properties of MoS2 photodetectors through reversible noncovalent functionalization" Chem. Comm., 2016 DOI: 10.1039/C6CC07678E Which has been published in final form at: http://pubs.rsc.org/en/content/articlelanding/2016/cc/c6cc07678e#!divAbstract photodetectors with the soluble PDI and tetraphenyl porphyrin (TPP) depicted in Chart 1. Here, we describe that the supramolecular functionalization of mechanically exfoliated MoS2-based photodetector...

Atomic-scale reproducibility and tunability endorse magnetic molecules as candidates for spin qubits and spintronics. A major challenge is to implant those molecular spins into circuit geometries that may allow one, two, or a few spins to be addressed in a controlled way. Here, the formation of mechanically bonded, magnetic porphyrin dimeric rings around carbon nanotubes (mMINTs) is presented. The mechanical bond places the porphyrin magnetic cores in close contact with the carbon nanotube without disturbing their structures. A combination of spectroscopic techniques shows that the magnetic geometry of the dimers is preserved upon formation of the macrocycle and the mMINT. Moreover, the metallic core selection determines the spin location in the mMINT. The suitability of mMINTs as qubits is explored by measuring their quantum coherence times (T m). Formation of the dimeric ring preserves the T m found in the monomer, which remains in the μs scale for mMINTs. The carbon nanotube is used as vessel to place the molecules in complex circuits. This strategy can be extended to other families of magnetic molecules. The size and composition of the macrocycle can be tailored to modulate magnetic interactions between the cores and to introduce magnetic asymmetries (heterometallic dimers) for more complex molecule-based qubits.

Abstract:The easily accessible benzofuran skeleton has been used as a platform for building two synthetic receptors able to associate with carboxylic acids and dinitrobenzoyl-substituted (DNB) amino acids. The synthesis of the benzofuran framework allows for functionalization with hydrogen bond binding sites such as amide and sulfonamide units, in a straightforward way. Substrates containing carboxylic acids are bound in the receptor cleft by multiple H-bonding interactions. The resulting associations can be further stabilized when new interactions such as aromatic π-π stacking are established. These binding inter-