1,10-phenanthroline entails several appealing structural and chemical properties: rigidity, planarity, aromaticity, basicity, chelating capability. This makes it a versatile starting material for synthetic organic, inorganic and supramolecular chemistry. In this tutorial review we examine how the chemical versatility of pristine 1,10-phenanthroline, a weakly fluorescent molecule, has been exploited to design many UV-Vis-NIR luminescent organic derivatives and coordination compounds with transition-metal (Ru(ii), Os(ii), Rh(iii), Cr(iii), Pt(ii), Zn(ii), Cu(i), Ag(i)) and rare-earth (Eu(iii),Tb(iii), Yb(iii), Nd(iii), Er(iii)) cations. They are utilized for many analytical and technological applications.

A H-bond-driven, noncovalent, reversible solubilization/functionalization of multiwalled carbon nanotubes (MWCNTs) in apolar organic solvents (CHCl(3), CH(2)Cl(2), and toluene) has been accomplished through a dynamic combination of self-assembly and self-organization processes leading to the formation of supramolecular polymers, which enfold around the outer wall of the MWCNTs. To this end, a library of phenylacetylene molecular scaffolds with complementary recognition sites at their extremities has been synthesized. They exhibit triple parallel H-bonds between the NH-N-NH (DAD) functions of 2,6-di(acetylamino)pyridine and the CO-NH-CO (ADA) imidic groups of uracil derivatives. These residues are placed at 180° relative to each other (linear systems) or at 60°/120° (angular modules), in order to tune their ability of wrapping around MWCNTs. Molecular Dynamics (MD) simulations showed that the formation of the hybrid assembly MWCNT•[X•Y](n) (where X = 1a or 1b -DAD- and Y = 2, 3, or 4 -ADA-) is attributed to π-π and CH-π interactions between the graphitic walls of the carbon materials and the oligophenyleneethynylene polymer backbones along with its alkyl groups, respectively. Addition of polar or protic solvents, such as DMSO or MeOH, causes the disruption of the H-bonds with partial detachment of the polymer from the CNTs, followed by precipitation. Taking advantage of the chromophoric and luminescence properties of the molecular subunits, the solubilization/precipitation processes have been monitored by UV-vis absorption and luminescence spectroscopies. All hybrid MWCNTs-polymer materials have been also structurally characterized via thermogravimetric analysis (TGA), transmission electron microscopy (TEM), atomic force microscopy (AFM), scanning tunneling microscopy (STM), and X-ray photoelectron spectroscopy (XPS).

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Luminescent carbon-based materials have been prepared by electrostatic self-assembly of negatively-charged luminescent Eu(III)-complex with imidazolium-functionalized MWCNTs.

The self-assembly and self-organization behavior of chromophoric acetylenic scaffolds bearing 2,6-bis(acetylamino)pyridine (1, 2) or uracyl-type (3-9) terminal groups has been investigated by photophysical and microscopic methods. Systematic absorption and luminescence studies show that 1 and 2, thanks to a combination of solvophilic/solvophobic forces and π-π stacking interactions, undergo self-organization in apolar solvents (i.e., cyclohexane) and form spherical nanoparticles, as evidenced by wide-field optical microscopy, TEM, and AFM analysis. For the longer molecular module, 2, a more uniform size distribution is found (80-200 nm) compared to 1 (20-1000 nm). Temperature scans in the range 283-353 K show that the self-organized nanoparticles are reversibly formed and destroyed, being stable at lower temperatures. Molecular modules 1 and 2 were then thoroughly mixed with the complementary triply hydrogen-bonding units 3-9. Depending on the specific geometrical structure of 3-9, different nanostructures are evidenced by microscopic investigations. Combination of modules 1 or 2 with 3, which bears only one terminal uracyl unit, leads to the formation of vesicular structures; instead, when 1 is combined with bis-uracyl derivative 4 or 5, a structural evolution from nanoparticles to nanowires is observed. The length of the wires obtained by mixing 1 and 4 or 1 and 5 can be controlled by addition of 3, which prompts transformation of the wires into shorter rods. The replacement of linear system 5 with the related angular modules 6 and 7 enables formation of helical nanostructures, unambiguously evidenced by AFM. Finally, thermally induced self-assembly was studied in parallel with modules 8 and 9, in which the uracyl recognition sites are protected with tert-butyloxycarbonyl (BOC) groups. This strategy allows further control of the self-assembly/self-organization process by temperature, since the BOC group is completely removed on heating. Microscopy studies show that the BOC-protected ditopic modules 8 self-assemble and self-organize with 1 into ordered linear nanostructures, whereas BOC-protected tritopic system 9 gives rise to extended domains of circular nano-objects in combination with 1.

The photophysical properties of a supramolecular fullerene-porphyrin ensemble resulting from the self-assembly of a pyrrolidinofullerene-imidazole derivative (F1) with a multimetalloporphyrin array constructed around a hexasubstituted fullerene core (F(ZnP)12) have been investigated. The fullerene hexa-adduct core of the host system does not play any active role in the cascade of photoinduced events of the supramolecular ensemble, indeed no intercomponent photoinduced processes could be observed in host F(ZnP)12. In contrast, upon axial coordination with the monosubstituted fullerene guest F1, a quantitative quenching of the fluorescence signal of the metalloporphyrins was observed for the supramolecular complex [F(ZnP)12(F1)n] both in polar and nonpolar solvents. In toluene, the supramolecular ensemble exhibits a charge transfer emission centered around nm, suggesting the occurrence of intramolecular face-to-face interactions of F1 with neighboring metalloporphyrin moieties within the self-assembled photoactive array. This mechanism is supported by the fact that a one order of magnitude increase in the binding constant was observed for the supramolecular complex [F(ZnP)12(F1)n] when compared with a reference system lacking the pyrrolidinofullerene unit. In benzonitrile, a long-lived charge-separated state (τ=0.3 μs) has been detected for the supramolecular adduct.

Microscopic and spectroscopic analysis of multiple types of nanocrystal formation in a one pot seedless and surfactantless procedure.

Chromophoric acetylenic scaffolds bearing complementary uracyl and 2,6-di(acetylamino)pyridyl moieties undergo supramolecular recognition and generate uniform nanoparticles, as observed by UV-Vis, AFM and TEM measurements.