Rare-earth-based metal–organic frameworks (ReMOFs) have emerged as an interesting family of compounds, for which new properties are increasingly being found. Based on the potential of ReMOFs, resulting from their optical properties, large numbers of investigations have been carried out during the last decade. Among these investigations, ReMOFs as optical sensors, using their luminescence properties, are increasingly becoming an attractive and useful topic of research. In this study, we have provided the basics of the luminescence behaviour of ReMOFs, various possible sensing mechanisms, and a summary of the uses of ReMOFs for the sensing of nitro explosives, cations, anions, small molecules, pH, and temperature.

Luminescent rare-earth-based MOFs as optical sensors

1-Hydroxypyrene (1-HP), which is a biomarker of polycyclic aromatic hydrocarbons (PAHs) carcinogens and represents the internal dose of PAHs exposure in the human body, is detected by a newly designed luminescent Eu-functionalized metal-organic framework (1a) sensor. The luminescence of 1a can be effectively quenched by 1-HP via a fluorescent resonant energy transfer process, thus achieving its recognition of 1-HP. This is the first use of lanthanide metal-organic frameworks (Ln-MOFs) as chemical sensors for 1-HP. The probe exhibits outstanding performances for sensing 1-HP, such as high selectivity, excellent sensitivity, fast response, and good reusability. Importantly, the sensing system enables the detection of 1-HP in real human urine specimens, and a portable 1-HP urine test paper is also developed. Hence, the reported 1-HP sensing platform has promising application potential for clinical diagnosis of the intoxication level of PAHs.

Determination of Urinary 1-Hydroxypyrene for Biomonitoring of Human Exposure to Polycyclic Aromatic Hydrocarbons Carcinogens by a Lanthanide-functionalized Metal-Organic Framework Sensor

Metal–organic frameworks (MOFs) hold tremendous promise for various academic and industrial applications because of their structural merits (e.g., high surface areas, enormous porosity, and regular order). Recently, processable MOF films have been sought for applications in various technologies, from separation to sensor devices. Essentially, MOFs deposited as thin films, with thicknesses ranging from nanometres to micrometres, low roughness and high homogeneity, are important for practical use and application-specific configurations, particularly in sensors and electric devices. Several innovative scientific methods have been developed for preparing MOF thin films. Among these methods, the electrochemical method is advantageous because it requires mild preparation, uses a short growth time, is easy to scale up and allows for controlling the phase/morphology and thickness by altering voltages in the process of fabricating uniform and dense MOF thin films. This review focuses on recent developments in electrochemical methods for forming metal–organic framework thin films (e.g., preparation, growth mechanisms and characterization techniques) and their corresponding applications in sensing and micro-pattern devices and identifies the challenges that must be overcome.

Metal–organic framework thin films: electrochemical fabrication techniques and corresponding applications & perspectives

A 2D zinc(II) metal–organic framework (Zn-MOF-1) formulated as [Zn(L)(H2O)]·H2O (1) (H2L = 5-(2-methylpyridin-4-yl)isophthalic acid) with blue fluorescence has been successfully obtained under hydrothermal conditions. Zn-MOF-1 contains microporous parallelogram channels with accessible Lewis-base sites, coordinated water molecules and uncoordinated carboxylates, which are easy to anchor and recognise various analytes. The fluorescence investigations demonstrated that the blue-light-emitting behaviour of Zn-MOF-1 possesses excellent water and pH stability. More importantly, this is the first reported recyclable multi-responsive Zn-MOF fluorescence sensor for Cr(III), Cr(VI) (CrO42−/Cr2O72− ions) and 4-NP (4-nitrophenol) simultaneously with high selectivity and sensitivity and low detection limits in aqueous solution through fluorescence quenching. Furthermore, the mechanism for the selective sensing of Cr3+, CrO42−, Cr2O72− or 4-NP can mainly be explained by the competition between the absorption of the analytes and the excitation/emission of Zn-MOF-1, and the electronic interactions between Zn-MOF-1 and the analytes.

An ultrastable zinc(II)–organic framework as a recyclable multi-responsive luminescent sensor for Cr(III), Cr(VI) and 4-nitrophenol in the aqueous phase with high selectivity and sensitivity

A terbium(III) lanthanide–organic framework (534-MOF-Tb) with a green-emission signal was successfully obtained by the solvothermal reaction of Tb3+ ions with the organic ligand H3TBOT (2,4,6-tris[1-(3-carboxylphenoxy)ylmethyl]mesitylene). 534-MOF-Tb contains microporous quadrangle channels with accessible Lewis-base sites and coordinated water molecules, which are feasible to anchor and recognise multifarious analytes. It can serve as a recyclable multi-responsive sensing material for detecting Fe3+, MnO4−, Cr2O72−, and p-nitrotoluene (4-NT). Significantly, this is the first reported MOF-based sensor for detecting explosive 4-NT. Moreover, the mechanism of the selective luminescence quenching response for Fe3+, MnO4−, Cr2O72− or 4-NT can be mainly explained in terms of the competition between the absorption of the light source energy and the electronic interaction between the analyte and the TBOT ligand.

A terbium(III) lanthanide–organic framework as a platform for a recyclable multi-responsive luminescent sensor

Rapid detection of nitroaromatic explosives is of utmost importance from the perspectives of civilian safety, the natural environment and human health. Herein, we design a simple yet powerful optical sensing motif based on an electrodeposited luminescent MOF thin film of {[Eu2(TDC)3(CH3OH)2]·CH3OH} (Eu-TDC, where TDC is thiophene-2,5-dicarboxylate). The parameters of the electrodeposition process were investigated and optimized. The phase and elemental composition of the Eu-TDC film were confirmed using powder X-ray diffraction (PXRD) and energy dispersive spectrometry (EDS), and its morphology and structure were examined using scanning electron microscopy (SEM). This thin film shows extremely good luminescence properties with characteristics of Eu3+ that are sensitized by the electron-rich ligands, which allows for high efficiency in electron-deficient nitroaromatic explosive sensing. Selective and sensitive responses to a series of nitroaromatic explosives were exhibited, especially for nitrophenols (TNP/DNP/4-NP, KSV > 104 M−1). It is also an efficient luminescent sensor for detecting nitrobenzene vapour. Significantly, this film can be easily recycled just by washing with methanol. The potential sensing mechanisms are discussed in detail.

A facile fabrication of electrodeposited luminescent MOF thin films for selective and recyclable sensing of nitroaromatic explosives.

A series of luminescent coatings of Tb3+ functionalized coordination polymers (CPs) consolidated by different multi-carboxylic ligands [1,4-benzenedicarboxylate, 1,3,5-benzenetricarboxylate, 2,6-naphthalenedicarboxylate] are fabricated on ZnO micronanoarrays. These hybrid luminescent coatings of Tb(III)@CPs/ZnO (Tb(III) functionalized CP/ZnO) are prepared by solvothermal synthesis and a postsynthetic functionalization (PSF) approach. Tb(III)@MOF-5/ZnO exhibits a highly detectable luminescence response for acetone molecules, and its structure, composition and morphology are characterized by XRD, EDS, ICP and SEM, respectively. It is first demonstrated that a lanthanide ion functionalized hybrid micronano-CP/ZnO coating is used as a small molecule sensor successfully.

Tb(III) postsynthetic functional coordination polymer coatings on ZnO micronanoarrays and their application in small molecule sensing

A luminescent Ln-CP film of [Tb2(BDC)3(H2O)4]n (1) [BDC: p-Benzenedicarboxylate anion] is fabricated using electrodeposition method on FTO (fluorine-doped tin oxide glass). It is a one-step and highly effective electrochemical method at room temperature. The influence of reaction conditions on the thickness of film 1 was investigated. A smooth and adherent thin film 1 is obtained at the appropriate concentrations of Tb(NO3)3 (0.01 M) and H2BDC (0.015 M) with 0.3 mA cm−2 (0.050 M NH4NO3) for 20 minutes. The composition of the film was confirmed by X-ray diffraction. The sensing properties of the film have been studied. The results show that thin film 1 exhibits selective detection of Cu2+ in DMF solution. The luminescent intensity is inversely proportional to the concentration of Cu2+ ions and displays a linear region over the range of 1 × 10−5 −1 × 10−3 M. Furthermore, a probable quenching mechanism is discussed.

One step cathodically electrodeposited [Tb2(BDC)3(H2O)4]n thin film as a luminescent probe for Cu2+ detection

A strong green-light-emitting Tb complex [Tb 2 (csal) 6 (H 2 O) 4 ]·4H 2 O ( 1 ) (Hcsal = 4-chlorosalicylicacid) has been synthesized. The structure was determined by single crystal X-ray diffraction. 1 exhibits a discrete dinuclear structure which is further assembled into a 3D supramolecular network by hydrogen bonding and aromatic π−π stacking interactions. This complex was used to detect ethylenediamine (EDA), triethylamine (TEA) and ethanolamine (EOA), the relationship between luminescence intense of 1 and concentrate of EDA or TEA can be fitted in Stern–Volmer equation. The results indicate that 1 is a promising probe for detecting amines with high selectivity and sensitivity.

A new dinuclear terbium complex as a novel luminescence probe for detecting amines

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Papers

A facile fabrication of electrodeposited luminescent MOF thin films for selective and recyclable sensing of nitroaromatic explosives.

Tb(III) postsynthetic functional coordination polymer coatings on ZnO micronanoarrays and their application in small molecule sensing

One step cathodically electrodeposited [Tb2(BDC)3(H2O)4]n thin film as a luminescent probe for Cu2+ detection

A new dinuclear terbium complex as a novel luminescence probe for detecting amines