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Postmodification of reticular materials with well‐defined catalysts is an appealing approach to produce new catalytic functional materials with improved stability and recyclability, but also to study catalysis in confined spaces. A promising strategy to this end is the postfunctionalization of crystalline and robust metal–organic frameworks (MOFs) to exploit the potential of crystal‐to‐crystal transformations for further characterization of the catalysts. In this regard, two new photocatalytic materials, MOF‐520‐PC1 and MOF‐520‐PC2, are straightforwardly obtained by the postfunctionalization of MOF‐520 with perylene‐3‐carboxylic acid (PC1) and perylene‐3‐butyric acid (PC2). The single crystal‐to‐crystal transformation yielded the X‐ray diffraction structure of catalytic MOF‐520‐PC2. The well‐defined disposition of the perylenes inside the MOF served as suitable model systems to gain insights into the photophysical properties and mechanism by combining steady‐state, time‐resolved, and transient absorption spectroscopy. The resulting materials are active organophotoredox catalysts in the reductive dimerization of aromatic aldehydes, benzophenones, and imines under mild reaction conditions. Moreover, MOF‐520‐PC2 can be applied for synthesizing gram‐scale quantities of products in continuous‐flow conditions under steady‐state light irradiation. This work provides an alternative approach for the construction of well‐defined, metal‐free, MOF‐based catalysts., We thank the ICIQ Foundation, the European Research Foundation for project ERC‐2014‐CoG 648304 (J.L.‐F.), MINECO (CTQ2016‐80038‐R; J.L.‐F.), and AGAUR 2017‐SGR‐1647 (J.L.‐F.) for funding. S.S.M. and N.K. are grateful to Marie‐Curie COFUND and JyC for postdoctoral scholarships, respectively.

An engineered hydrogel platform has been developed, in the absence of any toxic solvents or reagents, by the supramolecular self-assembly of three different components: a poly-β-cyclodextrin polymer, a hydrophobically modified dextran, and a photoactivatable bichromophoric molecular conjugate designed to photorelease nitric oxide (NO) with a fluorescent reporting function. The multivalent character of the interactions between the all components and the poor solubility of the conjugate in aqueous medium ensure the stability of the hydrogel and the lack of leaching of the photoactive cargo from the gel network under physiological conditions, even in the absence of protective coating agents. The photochemical properties of the molecular conjugate are retained in the supramolecular matrix, as demonstrated by the remote-controlled release of NO upon visible light excitation simultaneously to the activation of a fluorescent reporting function, which allows easy monitoring of the photoreleased NO.

Hybrid gold nanoclusters exhibiting photoregulated release of nitric oxide are obtained by appropriate self-assembling of a suitable host, a photoactivable guest and Au nanoparticles. The excitation of the core, the shell or both components of the nanoclusters with visible light, together with their dark stability and water solubility, make these nanoarchitectures intriguing candidates to be tested in biomedical research studies.

Modulation in the photophysical properties and intramolecular electron transfer behavior of the flavin adenine dinucleotide (FAD) molecule has been investigated in the presence of the macrocyclic hosts, alpha-, beta- and gamma-cyclodextrins (CDs), using absorption and steady-state and time-resolved fluorescence measurements. The results demonstrate that only the beta-CD host has a suitable cavity dimension to form a weak inclusion complex with FAD by encapsulating the adenine moiety, which is the preferred binding site in the large FAD molecule. Interestingly, in spite of the weak binding interaction, a significant enhancement in the fluorescence intensity of FAD is observed on complexation with beta-CD, and this has been attributed mainly to the modulation in the conformational dynamics of FAD in the presence of beta-CD. In aqueous solutions, a good fraction of FAD molecules exist in a "closed" conformation with the adenine and isoalloxazine rings stacked on each other, thus leading to very efficient fluorescence quenching due to the ultrafast intramolecular electron transfer from adenine to the isoalloxazine moiety. Complex formation with beta-CD inhibits this intramolecular electron transfer by changing the "closed" conformation of FAD to the "open" form, wherein the adenine and isoalloxazine moieties are widely separated, thus prohibiting the fluorescence quenching process. Further evidence for the conformational changes has been obtained by the observation of a long lifetime component in the fluorescence decay of FAD in the presence of beta-CD, which corresponds to the decay of the unquenched "open" form of FAD. Fluorescence up-conversion studies also indicate the absence of any ultrafast component in the fluorescence decay arising from the complexed FAD, thus supporting the formation of the "open" form in the presence of beta-CD, with no intramolecular electron transfer.

A non-fluorescent naphthalene diimide (NDI) dimer, conjugating red and blue NDI dyes, becomes red/NIR emitting upon G-quadruplex binding. The fluorescence lifetime which is significantly different for the complexes, the G-quadruplex/dimer and the weakly emitting ds-DNA/dimer is the key feature for the development of new rationally engineered G-quadruplex sensors.

We have developed a multifunctional biocompatible nanoconstruct based on polymeric nanoparticles encapsulating a molecular conjugate, able to photorelease nitric oxide (NO) with a fluorescent reporting function. We demonstrate that two-photon excitation (TPE) using biofriendly NIR 700 nm laser light can be applied for monitoring as well as triggering the release of NO, wherein the uncaging of a strongly fluorescent co-product acts in turn as a TPE fluorescent reporter for the simultaneous NO release from the nanoassembly. This supramolecular nanodevice internalizes in skin carcinoma cells, induces significant cell death upon light excitation and preserves its TPE properties, allowing the nearly instantaneous quantification of the NO photoreleased in cancer cells by two-photon NIR fluorescence microscopy.

We have developed herein an engineered polymer-based nanoplatform showing the convergence of two-photon fluorescence imaging and bimodal phototherapeutic activity in a single nanostructure. It was achieved through the appropriate choice of three different components: a β-cyclodextrin-based polymer acting as a suitable carrier, a zinc phthalocyanine emitting red fluorescence simultaneously as being a singlet oxygen ((1)O2) photosensitizer, and a tailored nitroaniline derivative, functioning as a nitric oxide (NO) photodonor. The self-assembly of these components results in photoactivable nanoparticles, approximately 35 nm in diameter, coencapsulating a multifunctional cargo, which can be delivered to carcinoma cells. The combination of steady-state and time-resolved spectroscopic and photochemical techniques shows that the two photoresponsive guests do not interfere with each other while being enclosed in their supramolecular container and can thus be operated in parallel under control of light stimuli. Specifically, two-photon fluorescence microscopy allows mapping of the nanoassembly, here applied to epidermal cancer cells. By detecting the red emission from the phthalocyanine fluorophore it was also possible to investigate the tissue distribution after topical delivery onto human skin ex vivo. Irradiation of the nanoassembly with visible light triggers the simultaneous delivery of cytotoxic (1)O2 and NO, resulting in an amplified cell photomortality due to a combinatory effect of the two cytotoxic agents. The potential of dual therapeutic photodynamic action and two-photon fluorescence imaging capability in a single nanostructure make this system an appealing candidate for further studies in biomedical research.

A multifunctional nanoplatform with four-in-one photoresponsive functionalities has been achieved through the co-encapsulation of two chromo-fluorogenic components within biocompatible polymeric nanoparticles. This engineered nanoconstruct efficiently delivers different photosensitizers in melanoma cells, which can be detected through their dual-color fluorescence, and induces amplified cell mortality due to the simultaneous photogeneration of singlet oxygen and nitric oxide.

Herein we report the design, preparation, and properties of a supramolecular system based on a tailored nitric oxide (NO) photodonor and a rhodamine-labeled β-cyclodextrin conjugate. The combination of spectroscopic and photochemical experiments shows the absence of significant interchromophoric interactions between the host and the guest in the excited states. As a result, the complex is able to release NO under the exclusive control of visible light, as unambiguously demonstrated by direct detection of this transient species through an amperometric technique, and exhibits the typical red fluorescence of the rhodamine appendage. The supramolecular complex effectively internalizes in HeLa cancer cells as proven by fluorescence microscopy, shows a satisfactory biocompatibility in the dark, and induces about 50% of cell mortality upon irradiation with visible light. The convergence of all these properties in one single complex makes the present host-guest ensemble an appealing candidate for further delevopment of photoactivatable nanoscaled systems addressed to photostimulated NO-based therapy.

We have developed a supramolecular nanoassembly capable of inducing remarkable levels of cancer cell mortality through a bimodal action based on the simultaneous photogeneration of nitric oxide (NO) and singlet oxygen ((1)O(2)). This was achieved through the appropriate incorporation of an anionic porphyrin (as (1)O(2) photosensitizer) and of a tailored NO photodonor in different compartments of biocompatible nanoparticles based on cationic amphiphilic cyclodextrins. The combination of steady-state and time-resolved spectroscopic techniques showed the absence of significant intra- and interchromophoric interaction between the two photoactive centers embedded in the nanoparticles, with consequent preservation of their photodynamic properties. Photodelivery of NO and (1)O(2) from the nanoassembly on visible light excitation was unambiguously demonstrated by direct and real-time monitoring of these transient species through amperometric and time-resolved infrared luminescence measurements, respectively. The typical red fluorescence of the porphyrin units was essentially unaffected in the bichromophoric nanoassembly, allowing its localization in living cells. The convergence of the dual therapeutic action and the imaging capacities in one single structure makes this supramolecular architecture an appealing, multifunctional candidate for applications in biomedical research.