Engineering Porosity and Functionality in a Robust Twofold Interpenetrated Bismuth-Based MOF: Toward a Porous, Stable, and Photoactive Material.

Defect engineering in metal-organic frameworks (MOFs) has gained worldwide research traction, as it offers tools to tune the properties of MOFs. Herein, we report a novel 2-fold interpenetrated Bi-based MOF made of a tritopic flexible organic linker, followed by missing-linker defect engineering. This procedure creates a gradually augmented micro- and mesoporosity in the parent (originally nonporous) network. The resulting MOFs can tolerate a remarkable extent of linker vacancy (with absence of up to 60% of linkers per Bi node) created by altering the crystal-growth rate as a function of synthesis temperature and duration. Owing to the enhanced porosity and availability of the uncoordinated Lewis acidic Bi sites, the defect-engineered MOFs manifested improved surface areas, augmented CO2 and water vapor uptake, and catalytic activity. Parallel to this, the impact of defect engineering on the optoelectronic properties of these MOFs has also been studied, offering avenues for new applications.

Ratiometric dual-emitting thermometers based on rhodamine B dye-incorporated (nano) curcumin periodic mesoporous organosilicas for bioapplications.

This study explores the potential of combining periodic mesoporous organosilicas (PMOs) with a fluorescent dye to develop a ratiometric thermometry system with enhanced stability, sensitivity, and biocompatibility. PMOs, ordered porous materials known for their stability and versatility, serve as an ideal platform. Curcumin, a natural polyphenol and fluorescent dye, is incorporated into PMOs to develop curcumin-functionalized PMOs (C-PMO) and curcumin-pyrazole-functionalized PMOs (CP-PMO) via hydrolysis and co-condensation. These PMOs exhibit temperature-dependent fluorescence properties. The next step involves encapsulating rhodamine B (RhB) dye within the PMO pores to create dual-emitting PMO@dye nanocomposites, followed by a lipid bilayer (LB) coating to enhance biocompatibility and dye retention. Remarkably, within the physiological temperature range, C-PMO@RhB@LB and CP-PMO@RhB@LB demonstrate noteworthy maximum relative sensitivity (Sr) values of up to 1.69 and 2.60% K-1, respectively. This approach offers versatile means to create various ratiometric thermometers by incorporating different fluorescent dyes, holding promise for future temperature sensing applications.

Versatile Palladium-catalyzed intramolecular cyclization to access new luminescent azaphosphaphenalene motifs.

Using a straightforward sequence of diphosphonylation and a Pd-catalysed concerted-metalation-deprotonation (CMD), a synthetic strategy towards polyaromatic phosphorus containing heterocycles was developed. Herein, we report the synthesis and characterization of new azaphosphaphenalenes, using easily accessible palladium catalysts and starting materials. The key tetrahydroquinoline intermediates of the reaction were synthesised via a fast and effective procedure and could be isolated as such, or further reacted towards the target polyaromatic structures. The obtained products showed interesting luminescent properties and their emission, excitation and quantum yields were evaluated.

Single-Crystal-to-Single-Crystal Photosynthesis of Supramolecular Organoboron Polymers with Dynamic Effects.

The solid-state synthesis of single-crystalline organic polymers, having functional properties, remains an attractive and developing research area in polymer chemistry and materials science. However, light-triggered topochemical synthesis of crystalline polymers comprising an organoboron backbone has not yet been reported. Here, we describe an intriguing example of single-crystal-to-single-crystal (SCSC) rapid photosynthesis (occurs on a seconds-scale) of two structurally different linear organoboron polymers, driven by environmentally sustainable visible/sun light, obtained from the same monomer molecule. A newly designed Lewis acid-base type molecular B ← N organoboron adduct (consisting of an organoboron core and naphthylvinylpyridine ligands) crystallizes in two solid-state forms featuring the same chemical structure but different 3D structural topologies, namely, monomers 1 and 2. The solvate molecule-free crystals of 1 undergo topochemical photopolymerization via an unusual olefin-naphthyl ring [2 + 2] cyclization to yield the single crystalline [3]-ladderane polymer 1P growing along the B ← N linkages, accompanied by instantaneous and violent macroscopic mechanical motions or photosalient effects (such as bending-reshaping and jumping motions). In contrast, visible light-harvesting single crystals of 2 quantitatively polymerize to a B ← N bond-stabilized polymer 2P in a SCSC fashion owing to the rapid [2 + 2] cycloaddition reaction among olefin double bonds. Such olefin bonds in the crystals of 2 are suitably preorganized for photoreaction due to the presence of solvate molecules in the crystal packing. Single crystals of 2 also show photodynamic jumping motions - in response to visible light but in a relatively slower fashion than the crystals of 1. In addition to SCSC topochemical polymerization and dynamic motions, both monomer crystals and their single-crystalline polymers feature green emissive and short-lived room-temperature phosphorescence properties upon excitation with visible-light wavelength.

Lanthanide-grafted hollow bipyridine-based periodic mesoporous organosilicas as chemical sensors.

We have synthesized a co-condensed hollow ethane-bipyridine periodic mesoporous organosilica (HEt-bpy-PMO) as a host material to anchor lanthanides for the purpose of developing a multifunctional chemical sensor. The host material was grafted with lanthanide chloride salts or complexes. The luminescence properties of the developed series of hybrid materials were studied in detail in the solid-state and after dispersing in water. The Eu3+ or Tb3+ singly incorporated materials were investigated for their use as ion sensors, showing ions selectivity towards Cu2+, Co2+ and Fe3+. Additionally, the Eu3+ or Tb3+ incorporated materials showed obvious luminescence quenching behavior towards acetone compared to other organic solvents, indicating excellent acetone sensing selectivity.

Turning 3D Covalent Organic Frameworks into Luminescent Ratiometric Temperature Sensors.

In this study, we report hybrid crystalline lanthanide-containing 3D covalent organic framework (Ln@3D COF) materials that are suitable for temperature sensing applications. Different routes to obtain these hybrid materials were tested and compared for material quality and thermometric properties. In the first approach, a bipyridine-containing 3D COF (Bipy COF) was grafted with a range of visible emitting lanthanide (Eu3+, Tb3+, Dy3+, and Eu3+/Tb3+) ß-diketonate complexes. In the second approach, a novel nanocomposite material was prepared by embedding NaYF4:Er,Yb nanoparticles on the surface of a nonfunctionalized 3D COF (COF-300). To the best of our knowledge, the luminescent materials developed here are the first 3D COFs to be tested as ratiometric temperature sensors. In fact, for the Bipy COF, two different types of thermometers were tested (the Eu3+/Tb3+ system and a rare Dy3+ system), with both showing excellent temperature sensing properties. The reported NaYF4:Er,Yb/COF-300 nanocomposite material combines upconverting nanoparticles with 3D COFs, similar to previously reported metal organic framework (MOF) nanocomposite materials; however, this type of hybrid material has not yet been explored for COFs. As such, our findings open a new pathway toward potential multifunctional materials that can combine thermometry with other modalities, such as catalysis or drug delivery, in just one nanocomposite material.

Visible Light-fueled Mechanical Motions with Dynamic Phosphorescence Induced by Topochemical [2+2] Reactions in Organoboron Crystals.

In the quest for essential energy solutions towards an ecological friendly future, the transformation of visible light/solar energy into mechanical motions in metal-free luminescent crystals offers a sustainable choice of smart materials for lightweight actuating, and all-organic electronic devices. Such green energy-triggered photodynamic motions with room temperature phosphorescence (RTP) emission in molecular crystals have not been reported yet. Here, we demonstrate three new stoichiometrically different Lewis acid-base molecular organoboron crystals (PS1, PS2, and PS3), which exhibit rapid photosalient effects (ballistic splitting, moving, and jumping) under both ultraviolet (UV) and visible light associated with quantitative single-crystal-to-single-crystal (SCSC) [2+2] cycloaddition of preorganized olefins. Furthermore, these systems respond to sunlight and mobile (white) flashlight with a complete SCSC transformation in a relatively slow fashion. Remarkably, all PS1, PS2, and PS3 crystals display visible light-promoted dynamic green RTP as their emission peaks promptly blue-shift, due to instantaneous photomechanical effects. Time-dependent structural mapping of intermediate photoproducts during fast SCSC [2+2] photoreaction, by X-ray photodiffraction, reveals a rationale for the origin of these photodynamic motions associated with rapid topochemical transformations. The reported light-driven behavior (mechanical motions, dynamic phosphorescence, and topochemical reactivity), is considered advantageous for the strategic design of stimuli-responsive multi-functional crystalline materials.

Photomechanical Motions in Organoboron-Based Phosphorescent Molecular Crystals Driven by a Crystal-State [2 + 2] Cycloaddition Reaction.

Photoluminescent molecular crystals integrated with the ability to transform light energy into macroscopic mechanical motions are a promising choice of materials for both actuating and photonic devices. However, such dynamic photomechanical effects, based on molecular organoboron compounds as well as phosphorescent crystalline materials, are not yet known. Here we present an intriguing example of photomechanical molecular single crystals of a newly synthesized organoboron containing Lewis acid-base molecular adduct (BN1, substituted triphenylboroxine and 1,2-di(4-pyridyl)ethylene) having a capsule shape molecular geometry. The single crystals of BN1 under UV light exhibit controllable rapid bending-shape recovery, delamination, violent splitting-jumping, and expanding features. The detailed structural investigation by single-crystal X-ray diffraction and 1H NMR spectroscopy reveals that the photosalient behavior of the BN1 single crystals is driven by a crystal-to-crystal [2 + 2] cycloaddition reaction, supported by four donor-acceptor type B←N bonds. The instant photomechanical reaction in the BN1 crystals occurs under UV on account of sudden release of stress associated with the strained molecular geometry, significant solid-state molecular movements (supramolecular change), and cleavage of half intermolecular B←N linkages to result in a complete photodimerized single-crystalline product via the existence of two other intermediate photoproducts. In addition, the BN1 crystals display short-lived room temperature phosphorescence, and the photodynamic events are accompanied by the enhancement of their phosphorescence intensity to yield the photoproduct. Interestingly, the molecular crystals of the final photoproduct polymerize at ambient conditions when recrystallized from the solution forming a 2D supramolecular crystalline polymer stabilized by the retention of all B←N coordination modes.

Dual-mode vehicles with simultaneous thermometry and drug release properties based on hollow Y2O3:Er,Yb and Y2O2SO4:Er,Yb spheres.

Employing luminescence thermometry in the biomedical field is undeniably appealing as many health conditions are accompanied by temperature changes. In this work, we show our ongoing efforts and results at designing novel vehicles for dual-mode thermometry and pH-dependent drug release based on hollow spheres. Hereby for that purpose, we exploit the hollow Y2O3 and Y2O2SO4 host materials. These two inorganic hollow phosphors were investigated and showed to have excellent upconversion Er3+-Yb3+ luminescence properties and could be effectively used as optical temperature sensors in the physiological temperature range when induced by near-infrared CW light (975 nm). Further, doxorubicin was exploited as a model anti-cancer drug to monitor the pH-dependent drug release of these materials showing that they can be used for simultaneous thermometry and drug delivery applications.

Deformation-induced phosphorescence shift in a 2D elastically flexible organic single crystal: role of chalcogen-centered weak interactions.

Mechanically responsive organic luminescent crystals are one of the promising choices of materials for flexible photonic devices. However, the change in phosphorescence emission as a function of the flexibility of a crystal has never been reported. Our current findings demonstrate two-dimensional (2D) and one-dimensional (1D) macroscopic elastic deformability, under mechanical stress, in elastically flexible single crystals of dibenzothiophene, and its brominated derivative, respectively. Unlike the presence of dual fluorescence (FL) and room temperature phosphorescence (RTP) in dibenzothiophene single crystals, the derivative was found to show only RTP. Interestingly, upon elastic deformation, single crystals of the dual emissive dibenzothiophene show a noticeable blue shift (∼20 nm) of RTP emission when compared to their pristine crystals (straight and naturally bent). However, their FL peaks remain nearly unchanged irrespective of the crystal deformation. A hierarchy of structure-elastic functionality to RTP modulation has been quantitatively mapped by rationalizing the role of chalcogen-involved weak interactions.

Unravelling the benefits of transition-metal-co-doping in lanthanide upconversion nanoparticles.

Recent advances reveal that upconversion (UC) luminescent materials are highly important not just from a scientific, but also from a future application standpoint. Although significant progress has been made in this field in recent decades, still their versatile applications are hindered by the low upconversion luminescence intensity and low tuneability, which has hampered further implementation in real life applications. We find it highly beneficial to compile a summary of recent relevant literature and propose ways to enhance upconversion efficiency in lanthanide nanomaterials. One very promising way to tackle this problem is through implementing transition metal ion co-dopants into the materials, which is the focus of this tutorial review. In this review, the recent studies related to the tailored design of UC materials with transition metal ion co-dopants have been summarized, and the desirable functionality of transition metal ions in the host matrixes has been discussed. Apart from improving the upconversion efficiency, the implementation of transition metal-co-dopants into lanthanide upconversion materials has recently sparked interest in applications such as in vivo imaging, drug delivery or nanothermometers.

Chemical sensors based on periodic mesoporous organosilica @NaYF4:Ln3+ nanocomposites.

Here, three unique organic-inorganic hybrid nanocomposite materials prepared by combining NaYF4:Yb3+,Ln3+ (Ln3+ = Er3+, Tm3+, Ho3+) and periodic mesoporous organosilica (PMO) are proposed for both metal ion sensing and solvent sensing. The luminescence properties of the developed hybrid materials, PMO@NaYF4:Yb3+,Ln3+, were studied in detail in the solid state and after dispersing in water. It is found that PMO@NaYF4:Yb3+,Er3+ showed selective "turn on" luminescence for Hg2+ with the detection limit of 24.4 µM in an aqueous solution. Additionally, the above three materials showed different luminescence emission responses towards water and organic solvents. It is worth noting that all three PMO@NaYF4:Yb3+,Ln3+ materials showed "turn on" luminescence towards alcohols. PMO@NaYF4:Yb3+,Er3+ and PMO@NaYF4:Yb3+,Ho3+ were selected and further developed into sensitive sensors for the detection of water in alcohols by taking advantage of their quenching behavior in water. The detection limit for sensing of water was determined to be 0.21%, 0.18% and 0.29%, corresponding to isopropanol (PMO@NaYF4:Yb3+,Er3+), n-butanol (PMO@NaYF4:Yb3+,Er3+) and ethanol (PMO@NaYF4:Yb3+,Ho3+), respectively. The above results illustrate the potential of these hybrid materials for applications in environmental fields as well as in chemical industries.

Ratiometric Thermometers Based on Rhodamine B and Fluorescein Dye-Incorporated (Nano) Cyclodextrin Metal-Organic Frameworks.

Macro- and nanosized core, as well as core-shell, γ-cyclodextrin metal-organic frameworks (γ-CD-MOFs) have been designed and used as platforms for the encapsulation of dye molecules to develop the first CD-MOF-based ratiometric optical thermometer materials. A novel dye combination was employed for this purpose, i.e., the duo rhodamine B (RhB) and fluorescein (FL). RhB is highly temperature-sensitive, whereas FL is less temperature-sensitive, and its luminescence emission peak is used as a reference. Promising results in terms of thermometric properties were obtained for a series of dye-encapsulated γ-CD-MOF materials based on this dye combination, with high relative sensitivities, even up to 5%K-1, for the dye-encapsulated 75%RhB-25%FL nanosized γ-CD-MOF, among the highest performance values reported so far for luminescent dual thermometers. In our study, we have additionally developed a simple yet effective preparation method for core-shell γ-CD-MOFs, allowing effective manipulation of the γ-CD-MOF shell growth. The proposed method allows incorporation of the FL and RhB dyes in the γ-CD-MOFs in a more controlled manner, enhancing the efficiency of the developed ratiometric (macro) γ-CD-MOF thermometers.

The importance, status, and perspectives of hybrid lanthanide-doped upconversion nanothermometers for theranostics.

Theranostics combines diagnostics and therapy in a single multifunctional system. Multifunctional upconversion luminescent lanthanide-doped nanothermometers for theranostic purposes offer non-invasive and sensitive multimodal performance in the biomedical field over traditional temperature measurement methods. Despite existing challenges, various studies on hybrid upconversion nanothermometers show substantial progress for (bio)imaging, temperature sensing, photodynamic and photothermal therapy, as well as drug delivery applications. The beauty of such an approach is that it unfolds possibilities to combine diagnostics and therapy in a single particle, which can modify the way certain diseases are treated, hence change the entire healthcare scene.

Upconverting Er3+-Yb3+ Inorganic/Covalent Organic Framework Core-Shell Nanoplatforms for Simultaneous Catalysis and Nanothermometry.

Lanthanide-based luminescent nanoparticles that are thermally responsive can be used to probe temperature changes at a nanoscale regime. However, materials that can work as both a nanothermometer and a catalyst are limited. Herein, we show that covalent organic frameworks (COFs), which is an emerging class of porous crystalline materials, can be grown around lanthanide nanoparticles to create unique core-shell nanostructures. In this way, the COF (shell) supports copper metal ions as catalytic sites and simultaneously lanthanide nanoparticles (ß-NaLuF4:Gd,Er,Yb-core) locally measure the temperature during the catalytic reaction. Moreover, ß-NaLuF4:Gd,Er,Yb nanoparticles are upconverting materials and hence can be excited at longer wavelengths (975 nm), which do not affect the catalysis substrates or the COF. As a proof-of-principle, a three-component addition reaction of benzaldehyde, indole, and malononitrile was studied. The local temperature was probed using luminescence nanothermometry during the catalytic reaction.

Chemical sensors based on a Eu(iii)-centered periodic mesoporous organosilica hybrid material using picolinic acid as an efficient secondary ligand.

Through a series of post synthetic modification methods applied to the 100% trans ethenylene-bridged Periodic Mesoporous Organosilica (ePMO), the lanthanide-functionalized hybrid nanomaterial ePMO@Eu_PA (PA = picolinic acid) has been prepared. The pristine and lanthanide-grafted ePMO materials were characterized by powder X-ray diffraction, DRIFTs, TGA, N2 sorption, SEM and TEM. The selected PA ligand could effectively sensitize the Eu3+ ion, leading to the characteristic luminescence of Eu3+ in ePMO@Eu_PA. The luminescence properties of the ePMO@Eu_PA were studied in detail in the solid state and after dispersing in water. The material was investigated for the use as ion sensor and showed a selective monitoring of Fe3+, Co2+ and Cu2+ ions with luminescence quenching. In addition, the material showed a linear relationship between the luminescence intensity and the pH value in the pH range from 7.7 to 10.2. These findings demonstrate that ePMO@Eu_PA possesses potential practical applications in ion sensing as well as in pH sensing.

Overview of N-Rich Antennae Investigated in Lanthanide-Based Temperature Sensing.

The market share of noncontact temperature sensors is expending due to fast technological and medical evolutions. In the wide variety of noncontact sensors, lanthanide-based temperature sensors stand out. They benefit from high photostability, relatively long decay times and high quantum yields. To circumvent their low molar light absorption, the incorporation of a light-harvesting antenna is required. This Review provides an overview of the nitrogen-rich antennae in lanthanide-based temperature sensors, emitting in the visible light spectrum, and discusses their temperature sensor ability. The N-rich ligands are incorporated in many different platforms. The investigation of different antennae is required to develop temperature sensors with diverse optical properties and to create a diverse offer for the multiple application fields. Molecular probes, consisting of small molecules, are first discussed. Furthermore, the thermometer properties of ratiometric temperature sensors, based on di- and polynuclear complexes, metal-organic frameworks, periodic mesoporous organosilicas and porous organic polymers, are summarized. The antenna mainly determines the application potential of the ratiometric thermometer. It can be observed that molecular probes are operational in the broad physiological range, metal-organic frameworks are generally very useful in the cryogenic region, periodic mesoporous organosilica show temperature dependency in the physiological range, and porous organic polymers are operative in the cryogenic-to-medium temperature range.

Rational design of lanthanide nano periodic mesoporous organosilicas (Ln-nano-PMOs) for near-infrared emission.

We present three Periodic Mesoporous Organosilica (PMO) materials: a PMO material functionalized with pyridine dicarboxamide (DPA-PMO) and two amine functionalized PMO materials (Am-PMO and Am-ePMO). The pyridine dicarboxamide ligands in the DPA-PMO material provide the tethering sites for Ln3+-coordination. A Schiff base reaction was carried out on the amine functionalized PMOs to introduce similar lanthanide coordination sites. The Nd and Yb modified nano-PMOs are evaluated as near-infrared (NIR) emitting luminescent materials. The DPA-PMO and Am-ePMO materials can act as good platforms for NIR luminescence. A significant enhancement in the decay time can be observed upon grafting an Yb(hfa)3 complex to the PMO materials instead of YbCl3. All of the DPA-PMO@Ln(hfa)3 and Am-ePMO@Ln(hfa)3 materials show characteristic NIR emission performance both in the solid state and in aqueous suspension.

Luminescent PMMA Films and PMMA@SiO2 Nanoparticles with Embedded Ln3+ Complexes for Highly Sensitive Optical Thermometers in the Physiological Temperature Range*.

In recent years, luminescent materials doped with Ln3+ ions have attracted much attention for their application as optical thermometers based on both downshifting and upconversion processes. This study presents research done on the development of highly sensitive optical thermometers in the physiological temperature range based on poly(methyl methacrylate) (PMMA) films doped with two series of visible Ln3+ complexes (Ln3+ =Tb3+ , Eu3+ , and Sm3+ ) and SiO2 nanoparticles (NPs) coated with these PMMA films. The best performing PMMA film doped with Tb3+ and Eu3+ complexes was the PMMA[TbEuL1 tppo]1 film (L1 =4,4,4-trifluoro-1-phenyl-1,3-butadionate; tppo=triphenylphosphine oxide), which showed good temperature sensing of Sr =4.21 % K-1 at 313 K, whereas for the PMMA films doped with Tb3+ and Sm3+ complexes the best performing was the PMMA[TbSmL2 tppo]3 film (L2 =4,4,4-trifluoro-1-(4-chlorophenyl)-1,3-butadionate), with Sr =3.64 % K-1 at 313 K. Additionally, SiO2 NPs coated with the best performing films from each of the series of PMMA films (Tb-Eu and Tb-Sm) and their temperature-sensing properties were studied in water, showing excellent performance in the physiological temperature range (PMMA[TbEuL1 tppo]1@SiO2 : Sr =3.84 % °C at 20 °C; PMMA[TbSmL2 tppo]3@SiO2 : Sr =3.27 % °C at 20 °C) and the toxicity of these nanoparticles on human cells was studied, showing that they were nontoxic.

Luminescent Ratiometric Thermometers Based on a 4f-3d Grafted Covalent Organic Framework to Locally Measure Temperature Gradients During Catalytic Reactions.

Covalent Organic Frameworks (COFs), an emerging class of crystalline porous materials, are a new type of support for grafting lanthanide ions (Ln3+ ), which can be employed as ratiometric luminescent thermometers. In this work we have shown that COFs co-grafted with lanthanide ions (Eu3+ , Tb3+ ) and Cu2+ (or potentially other d-metals) can synchronously be employed both as a nanothermometer and catalyst during a chemical reaction. The performance of the thermometer could be tuned by changing the grafted d-metal and solvent environment. As a proof of principle, the Glaser coupling reaction was investigated. We show that temperature can be precisely measured during the course of the catalytic reaction using luminescence thermometry. This concept could be potentially easily extended to other catalytic reactions by grafting other d-metal ions on the Ln@COF platform.