Injectable hydrogels have received considerable interest in the biomedical field due to their potential applications in minimally invasive local drug delivery, more precise implantation, and site‐specific drug delivery into poorly reachable tissue sites and into interface tissues, where wound healing takes a long time. Injectable hydrogels, such as in situ forming and/or shear‐thinning hydrogels, can be generated using chemically and/or physically crosslinked hydrogels. Yet, for controlled and local drug delivery applications, the ideal injectable hydrogel should be able to provide controlled and sustained release of drug molecules to the target site when needed and should limit nonspecific drug molecule distribution in healthy tissues. Thus, such hydrogels should sense the environmental changes that arise in disease states and be able to release the optimal amount of drug over the necessary time period to the target region. To address this, researchers have designed stimuli‐responsive injectable hydrogels. Stimuli‐responsive hydrogels change their shape or volume when they sense environmental stimuli, e.g., pH, temperature, light, electrical signals, or enzymatic changes, and deliver an optimal concentration of drugs to the target site without affecting healthy tissues.

The spectroscopic and electrochemical behavior as well as electrogenerated chemiluminescence (ECL) of a series of donor-π-donor derivatives bearing triphenylamine groups as donor connected to a fluorene, 2,7-bis-(4-(N,N-diphenylamino)phen-1-yl)-9,9'-dimethylfluorene (1), or spirobifluorene core, 2,7-bis-(4-(N,N-diphenylamino)phen-1-yl)-9,9'-spirobifluorene (2) and 2,2',7,7'-tetrakis(4-(N,N-diphenylamino)phen-1-yl)-9,9'-spirobifluorene (3), were investigated. Besides a high photoluminescence (PL) quantum yield in solution (between 81 and 87%), an efficient radical ions annihilation process induces intense greenish blue ECL emission that could be seen with the naked eye. Only the tetrasubstituted spirobifluorene derivative (compound 3) shows weak ECL obtained by a direct annihilation mechanism. Because the energy of the annihilation reaction is higher than the energy required to form the singlet excited state, the S-route could be considered the pathway followed by the ECL process in these molecules. The ECL emissions recorded by direct ion-ion annihilation show two bands compared to the single structureless PL band. The ECL spectra obtained by a coreactant approach using benzoylperoxide as a coreagent show no differences relative to that produced by annihilation, except for an increasing of ECL intensity for all compounds.

We describe the synthesis, computational analysis, photophysics, electrochemistry and electrochemiluminescence (ECL) of a series of compounds formed of two triphenylamines linked by a fluorene or spirobifluorene bridge. The phenylamine moieties were modified at the para-position of the two external rings by electron-withdrawing or electron-donating substituents. These modifications allowed for fine-tuning of the photoluminescence (PL) and ECL emission from blue to green, with an overall wavelength span of 73 (PL) and 67 (ECL) nm, respectively. For all compounds, we observed a very high PL quantum yield (79-89%) and formation of stable radical ions. The ECL properties were investigated by direct annihilation of the electrogenerated radical anion and radical cation. The radical-ion annihilation process is very efficient and causes an intense greenish-blue ECL emission, easily observable even by naked eye, with quantum yield higher than the standard 9,10-diphenylanthracene. The ECL spectra show one single band that almost matches the PL band. Because the energy of the annihilation reaction is higher than that required to form the singlet excited state, the S-route is considered the favored pathway followed by the ECL process in these molecules. All these features point to this type of molecular system as promising for ECL applications.

The design of innovative and more efficient Aggregation‐Induced Emission (AIE) chromophores has kept a very high scientific interest since the first report on 2001. Among the possible applications, the field of the organic electroluminescent diodes (OLEDs) is highly attractive. This review will focus on very recent development in the design of AIE molecules for OLEDs, with particular attention on the performance of different emitting devices. Another key point is the description of the new class of AIE luminogens showing Thermally Activated Delayed Fluorescence (TADF), which appears as possible solution to overcome the limitation of fluorescent dyes employed in electroluminescent devices.

The pinene-bipyridine carboxylic derivatives (+)- and (-)-HL, designed to form configurationally stable lanthanide complexes, proved their effectiveness as chiral building blocks for the synthesis of lanthanide-containing superstructures. Indeed a self-assembly process takes place with complete diastereoselectivity between the enantiomerically pure ligand L(-) and Ln(III) ions (La, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er), thus leading to the quantitative formation of a trinuclear supramolecular architecture with the general formula [Ln(3)(L)(6)(mu(3)-OH)(H(2)O)(3)](ClO(4))(2) (abbreviated as tris(Ln[L](2))). This class of C(3)-symmetrical compounds was structurally characterized in the solid state and solution. Electrospray (ES) mass spectrometric and (1)H NMR spectroscopic analyses indicated that the trinuclear species are maintained in solution (CH(2)Cl(2)) and are stable in the investigated concentration range (10(-2)-10(-6) m). The photophysical properties of the ligand HL and its tris(Ln[L](2)) complexes were studied at room temperature and 77 K, thus demonstrating that the metal-centered luminescence is well sensitized both for the visible and near-IR emitters. The chiroptical properties of tris(Ln[L](2)) complexes were investigated by means of circular dichroism (CD) and circularly polarized luminescence (CPL). A high CD activity is displayed in the region of pi-pi* transitions of bipyridine. CPL spectra of tris(Eu[(+)-L](2)) and tris(Tb[(+)-L](2)) present large dissymmetry factors g(em) for the sensitive transitions of Eu(III) ((5)D(0)-->(7)F(1), g(em)=-0.088) and Tb(III) ((5)D(4)-->(7)F(5), g(em)=-0.0806). The self-recognition capabilities of the system were tested in the presence of artificial enantiomeric mixtures of the ligand. (1)H NMR spectra identical to those of the enantiomerically pure complexes and investigations by CD spectroscopic analysis reveal an almost complete chiral self-recognition in the self-assembly process, thus leading to mixtures of homochiral trinuclear structures.

A new class of push-pull spirobifluorene compounds 1-5 has been synthesized. The nonlinear optical (NLO) properties (first and second hyperpolarizability β and γ, respectively) of spirobifluorene derivatives have been investigated for the first time using electric field induced second harmonic (EFISH) and third harmonic generation (THG) methods. Moreover, a comparison with the corresponding push-pull

Gelators are compounds capable of solidifying various solvents and water. Organic gels, and in particular hydrogels, are interesting soft materials with many potential applications. In this paper the formation of luminescent gels in water and dimethylformamide as solvents is reported. The gels are prepared by using a carboxylate‐based aliphatic gelator (1) and a N,N′‐bis(O‐methyl‐TyrOH) oxalamide derivative (2). The gels are transparent, and form fiberlike structures in the presence of the red luminescent moiety, a EuIII hemicaged complex. The spectroscopic behavior of the complex is investigated in different solvents and when is entrapped in the gel. In order to probe the involvement of the chemical structure of the luminescent moiety in the gel network, a ruthenium complex, Ru(bpy)2(dppz)2+ (where bpy = 2,2′‐bipyridine and dppz = dipyrido[3,2‐a:2′,3′‐c]phenazine) has also been employed. The complex is in fact nonluminescent in water, while emitting when incorporated in the gel. Such “switching on” behavior is attributed to the incorporation of the complex into the lipophilic environment of gel fibers, where it is shielded from quenching by water molecules.

Electrochemiluminescence (ECL) generated by a monolayer of a spirobifluorene derivative covalently bound onto an indium tin oxide (ITO) substrate is reported for the first time. Our approach allows the efficient preparation homogeneous and patterned substrates through micromolding in capillaries (MIMIC), and opens novel scenarios for multicolour ECL applications.