Templating Porphyrin Anisotropy via Magnetically Aligned Carbon Nanotubes

Abstract

The preparation and characterisation of a novel three‐dimensional organic material consisting of porphyrin arrays on carbon nanotubes embedded in an organogel is reported. Firstly, the porphyrin array was prepared through metal‐ligand coordination of a ditopic ligand (1,2‐bis(4‐pyridyl)ethane) and two bis‐Zn(II) porphyrins, linked through a pyrene core, and was studied through UV‐Vis, NMR and diffusion spectroscopies. Secondly, the porphyrin supramolecular architecture was adsorbed on pristine carbon nanotubes, greatly improving the dispersibility of the latter in organic solvents. The hybrid material was characterised by means of UV‐Vis spectroscopy, microscopic techniques and thermogravimetric analysis. Finally, by exploiting the anisotropic magnetic susceptibility of carbon nanotubes, the hybrid material was aligned under a magnetic field, the organisation of which could be maintained by in situ gelation. The resultant hybrid organogel exhibited notable optical anisotropy, suggesting an anisotropic arrangement of the porphyrin‐CNTs architectures in the macroscopic material.

Design, Synthesis, and Functionalization Strategies of Tailored Carbon Nanodots

“…46 In addition, we looked at supramolecular donor-acceptor architectures. 47,48 A library of positively charged porphyrins and carboxylic acid-coated (negatively charged) g-N-CDs was studied to assess the electrostatic interactions in guiding the formation of supramolecular assemblies and charge separation (Figure 8c,d). 49 Our studies highlight the potential of the CD tunable surface functionalities but, more importantly, such surface modification strategies, together with pre-synthetic schemes targeting modulation of the CD properties, could give a great contribution in extending the applicability of the CDs in various fields.…”

“…We prepared a hybrid material through an amidation (carbodiimide condensation) reaction of the amino surface groups of a -N-CDs with a carboxyphenyl peripheral moiety of a porphyrin (Figure a,b) . In addition, we took advantage of the well-established porphyrin pheripheral functionalization chemistry to prepare supramolecular donor–acceptor (nano)­architectures. , A library of positively charged porphyrins and carboxylic acid-coated (negatively charged) g -N-CDs was studied to assess the electrostatic interactions in guiding the formation of supramolecular assemblies and charge separation (Figure c,d) . Detailed photophysical characterization of the covalent and supramolecular hybrids showed markedly different behavior.…”

Self-assembly and spectroscopic fingerprints of photoactive pyrenyl tectons on hBN/Cu(111)

“…Pyrene derivatives are excellent candidates to study the interplay of functionalization and supramolecular organization as the planar polycyclic aromatic core provides an extended π-system that can be readily substituted at distinct positions [47][48][49][50][51][52][53][54]. With prominent fluorescence properties, pyrene is often considered the "fruitfly of photochemists", and several materials have been prepared for applications in optoelectronic devices and organic electronics [47].…”

Applications of Photoinduced Phenomena in Supramolecularly Arranged Phthalocyanine Derivatives: A Perspective

“…In order to associate the diverse moieties of such multimodular structures, various approaches are available (used individually and independently or in combination) and, among them, the ones enabling thorough management of molecular architecture are the most employed: dispersion forces [16], electrostatic attractions [11], hydrogen-bonding interactions [17], hydrophobic effects [18], Langmuir-Blodgett [19] and Langmuir-Schäfer [20] techniques, Layer-by-Layer transfer [21], metal to ligand coordination [22], π-π stacking interactions [23], physical evaporation [24] and ultra-high vacuum methods [25], self-assembly [26], van der Waals interactions [27], and so on. These are some of the preferred means for the preparation of supramolecular and multimodular structures with tunable characteristics.…”