Luminescent metal–organic frameworks as chemical sensors: common pitfalls and proposed best practices

The ever-increasing need to determine and monitor the chemical constituents of the constantly evolving environment has led the global scientific community to invest considerable research effort in the development of efficient and user-friendly chemical sensors. The development of improved chemical sensors largely depends on the synthesis of novel materials with the ability to transform a molecular recognition event into a readable signal. Among the various types of sensory materials, those where analyte detection is based on the change of a luminescence signal are gaining increasing attention due to the extremely high sensitivities which can be achieved in combination with new technological advances enabling the integration of optical detection systems in small, portable and easy to use devices. In this critical review we approach the emerging field of sensory materials based on luminescent metal–organic frameworks (LMOFs) by beginning with a survey of the general principles of luminescence-based sensing. In particular, after a brief overview, we first focus on the working principles and successes of well established sensory materials based on small molecules and conjugated polymers. Subsequently, we concentrate on the special features of LMOFs which make them promising sensory materials and we discuss best practices which researchers in the field should follow in order to prove the sensing ability of LMOFs and avoid common misconceptions and errors. We continue with presenting selected examples of LMOF-based sensors for nitroaromatics, humidity and heavy metal ions from the recent literature and we conclude with a summary of the state-of-the-art of LMOF sensors. Finally, we propose some directions for future research on LMOF sensors.

[1]  M. Allendorf,et al.  Reports of Meetings , 1970 .

[2]  P. Mukherjee,et al.  Modification of extended open frameworks with fluorescent tags for sensing explosives: competition between size selectivity and electron deficiency. , 2014, Chemistry.

[3]  R. Snurr,et al.  Modeling water and ammonia adsorption in hydrophobic metal-organic frameworks: Single components and mixtures , 2014 .

[4]  Svetlana V. Eliseeva,et al.  Near-infrared emitting probes for biological imaging: Organic fluorophores, quantum dots, fluorescent proteins, lanthanide(III) complexes and nanomaterials , 2017 .

[5]  Jinshun Zhao,et al.  Carcinogenicity of chromium and chemoprevention: a brief update , 2017, OncoTargets and therapy.

[6]  Lei You,et al.  Recent Advances in Supramolecular Analytical Chemistry Using Optical Sensing. , 2015, Chemical reviews.

[7]  Frances S. Ligler,et al.  Chemical and biological detection. , 2013, Chemical Society reviews.

[8]  Nathaniel L Rosi,et al.  Cation-triggered drug release from a porous zinc-adeninate metal-organic framework. , 2009, Journal of the American Chemical Society.

[9]  Qin Zhou,et al.  Method for enhancing the sensitivity of fluorescent chemosensors: energy migration in conjugated polymers , 1995 .

[10]  K. Müller‐Buschbaum,et al.  Lanthanide based tuning of luminescence in MOFs and dense frameworks--from mono- and multimetal systems to sensors and films. , 2014, Chemical communications.

[11]  Yu Ding,et al.  Novel Signal‐Amplifying Fluorescent Nanofibers for Naked‐Eye‐Based Ultrasensitive Detection of Buried Explosives and Explosive Vapors , 2012 .

[12]  Brian P. Mehl,et al.  Energy transfer dynamics in metal-organic frameworks. , 2010, Journal of the American Chemical Society.

[13]  T. Gunnlaugsson,et al.  Fluorescent chemosensors: the past, present and future. , 2017, Chemical Society reviews.

[14]  Georges Mouchaham,et al.  Titanium coordination compounds: from discrete metal complexes to metal-organic frameworks. , 2017, Chemical Society reviews.

[15]  W. Seitz,et al.  A fiber optic sensor for water in organic solvents based on polymer swelling. , 1994, Talanta.

[16]  T. Főrster,et al.  10th Spiers Memorial Lecture. Transfer mechanisms of electronic excitation , 1959 .

[17]  J. Williams,et al.  Lighting the way to see inside the live cell with luminescent transition metal complexes , 2012 .

[18]  Michael O’Keeffe,et al.  The Chemistry and Applications of Metal-Organic Frameworks , 2013, Science.

[19]  Pedro Pedro Gili= Pedro Gili Trujillo Gili,et al.  Equilibria of chromate(VI) species in acid medium and ab initio studies of these species , 1997 .

[20]  B. Yan,et al.  A water-stable lanthanide-functionalized MOF as a highly selective and sensitive fluorescent probe for Cd(2.). , 2015, Chemical communications.

[21]  O. Yaghi,et al.  Structures of Metal-Organic Frameworks with Rod Secondary Building Units. , 2016, Chemical reviews.

[22]  Cheng Wang,et al.  Diffusion-controlled luminescence quenching in metal-organic frameworks. , 2011, Journal of the American Chemical Society.

[23]  S. Baudron,et al.  Luminescent metal–organic frameworks based on dipyrromethene metal complexes and BODIPYs , 2016 .

[24]  G. Wiederrecht,et al.  Light-harvesting and ultrafast energy migration in porphyrin-based metal-organic frameworks. , 2013, Journal of the American Chemical Society.

[25]  J. Tusa,et al.  Critical care analyzer with fluorescent optical chemosensors for blood analytes , 2005 .

[26]  W. Zhou,et al.  Metal-Organic Frameworks as Platforms for Functional Materials. , 2016, Accounts of chemical research.

[27]  M. Cohen,et al.  Mechanisms of chromium carcinogenicity and toxicity. , 1993, Critical reviews in toxicology.

[28]  Dawei Feng,et al.  Construction of ultrastable porphyrin Zr metal-organic frameworks through linker elimination. , 2013, Journal of the American Chemical Society.

[29]  Yu Lei,et al.  Fluorescence based explosive detection: from mechanisms to sensory materials. , 2015, Chemical Society reviews.

[30]  Blessy B. Mathew,et al.  Toxicity, mechanism and health effects of some heavy metals , 2014, Interdisciplinary toxicology.

[31]  S. Eliseeva,et al.  Rare Earth pcu Metal-Organic Framework Platform Based on RE4(μ3-OH)4(COO)62+ Clusters: Rational Design, Directed Synthesis, and Deliberate Tuning of Excitation Wavelengths. , 2017, Journal of the American Chemical Society.

[32]  Omar M Yaghi,et al.  Metal insertion in a microporous metal-organic framework lined with 2,2'-bipyridine. , 2010, Journal of the American Chemical Society.

[33]  Linbing Sun,et al.  Metal-Organic Frameworks for Heterogeneous Basic Catalysis. , 2017, Chemical reviews.

[34]  David Fairen-Jimenez,et al.  Vapor-phase metalation by atomic layer deposition in a metal-organic framework. , 2013, Journal of the American Chemical Society.

[35]  Matthew W. Logan,et al.  Systematic Variation of the Optical Bandgap in Titanium Based Isoreticular Metal-Organic Frameworks for Photocatalytic Reduction of CO2 under Blue Light , 2017 .

[36]  Jing Li,et al.  Metal-organic frameworks: functional luminescent and photonic materials for sensing applications. , 2017, Chemical Society reviews.

[37]  William R. Dichtel,et al.  Direct detection of RDX vapor using a conjugated polymer network. , 2013, Journal of the American Chemical Society.

[38]  Shiguo Wang,et al.  Nanomaterials for luminescence detection of nitroaromatic explosives , 2015 .

[39]  G. Armatas,et al.  Selective capture of hexavalent chromium from an anion-exchange column of metal organic resin–alginic acid composite† †Electronic supplementary information (ESI) available: Synthesis procedures, experimental details of physical measurements, SEM images, thermal analysis, CO2 sorption data and pore s , 2015, Chemical science.

[40]  Dongpeng Yan,et al.  Lanthanide doped coordination polymers with tunable afterglow based on phosphorescence energy transfer. , 2017, Chemical communications.

[41]  Hai-Long Jiang,et al.  Chemical Sensors Based on Metal-Organic Frameworks. , 2016, ChemPlusChem.

[42]  R. Silbey,et al.  Quantitative relationship between analyte concentration and amplified signal intensity of a molecular wire sensor. , 2005, Analytical chemistry.

[43]  T. Swager Iptycenes in the design of high performance polymers. , 2008, Accounts of chemical research.

[44]  G. Wiederrecht,et al.  Metal-organic framework materials for light-harvesting and energy transfer. , 2015, Chemical communications.

[45]  P. Kovacic,et al.  Nitroaromatic compounds: Environmental toxicity, carcinogenicity, mutagenicity, therapy and mechanism , 2014, Journal of applied toxicology : JAT.

[46]  Li-Ping Lin,et al.  Efficient Capture and Effective Sensing of Cr2O72- from Water Using a Zirconium Metal-Organic Framework. , 2017, Inorganic chemistry.

[47]  Véronique Jubera,et al.  A facile building-block synthesis of multifunctional lanthanide MOFs , 2011 .

[48]  Max Costa,et al.  Toxicity and Carcinogenicity of Chromium Compounds in Humans , 2006 .

[49]  Lanthanide ion probes of structure in biology. Laser-induced luminescence decay constants provide a direct measure of the number of metal-coordinated water molecules , 1979 .

[50]  K. Müller‐Buschbaum,et al.  MOF based luminescence tuning and chemical/physical sensing , 2015 .

[51]  Zhengguo Zhu,et al.  Energy migration in conjugated polymers: the role of molecular structure , 2007, Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences.

[52]  M. Zaworotko Materials science: Designer pores made easy , 2008, Nature.

[53]  Michael O'Keeffe,et al.  Systematic Design of Pore Size and Functionality in Isoreticular MOFs and Their Application in Methane Storage , 2002, Science.

[54]  G. Rothenberg,et al.  Highly selective water adsorption in a lanthanum metal-organic framework. , 2014, Chemistry.

[55]  Lars Öhrström,et al.  Coordination polymers, metal-organic frameworks and the need for terminology guidelines , 2012 .

[56]  S. Seki,et al.  Excited-state intramolecular proton-transfer (ESIPT)-inspired solid state emitters. , 2016, Chemical Society reviews.

[57]  C. Su,et al.  Ultrafast water sensing and thermal imaging by a metal-organic framework with switchable luminescence , 2017, Nature Communications.

[58]  Z. Su,et al.  Efficient and tunable white-light emission of metal–organic frameworks by iridium-complex encapsulation , 2013, Nature Communications.

[59]  Zhiyu Wang,et al.  A Terbium Metal-Organic Framework for Highly Selective and Sensitive Luminescence Sensing of Hg2+ Ions in Aqueous Solution. , 2016, Chemistry.

[60]  Yongsheng Li,et al.  Porphyrinic MOFs for reversible fluorescent and colorimetric sensing of mercury(II) ions in aqueous phase , 2016 .

[61]  Jing Li,et al.  Luminescent metal-organic frameworks for chemical sensing and explosive detection. , 2014, Chemical Society reviews.

[62]  C. Tung,et al.  A Water-Stable Cl@Ag14 Cluster Based Metal-Organic Open Framework for Dichromate Trapping and Bacterial Inhibition. , 2017, Inorganic chemistry.

[63]  Abdullah M. Asiri,et al.  Metal-Organic Framework (MOF) Compounds: Photocatalysts for Redox Reactions and Solar Fuel Production. , 2016, Angewandte Chemie.

[64]  Cong Xu,et al.  A Multi-responsive Regenerable Europium-Organic Framework Luminescent Sensor for Fe3+ , CrVI Anions, and Picric Acid. , 2016, Chemistry.

[65]  Reena Singh,et al.  Heavy metals and living systems: An overview , 2011, Indian journal of pharmacology.

[66]  Yongkang Liang Automation of Karl Fischer water titration by flow injection sampling , 1990 .

[67]  Jie Su,et al.  Piezofluorochromic Metal-Organic Framework: A Microscissor Lift. , 2015, Journal of the American Chemical Society.

[68]  Seth M Cohen,et al.  Isoreticular synthesis and modification of frameworks with the UiO-66 topology. , 2010, Chemical communications.

[69]  Brian P. Mehl,et al.  Triplet Excitation Energy Dynamics in Metal–Organic Frameworks , 2013 .

[70]  Giannis S. Papaefstathiou,et al.  Turn-on luminescence sensing and real-time detection of traces of water in organic solvents by a flexible metal-organic framework. , 2015, Angewandte Chemie.

[71]  Carlo Lamberti,et al.  A new zirconium inorganic building brick forming metal organic frameworks with exceptional stability. , 2008, Journal of the American Chemical Society.

[72]  Chuande Wu,et al.  Porous metal-organic frameworks for heterogeneous biomimetic catalysis. , 2014, Accounts of chemical research.

[73]  Hangxun Xu,et al.  Coordination chemistry in the design of heterogeneous photocatalysts. , 2017, Chemical Society reviews.

[74]  M. Dincǎ,et al.  Postsynthetic tuning of hydrophilicity in pyrazolate MOFs to modulate water adsorption properties , 2013 .

[75]  Omar M Yaghi,et al.  Water adsorption in porous metal-organic frameworks and related materials. , 2014, Journal of the American Chemical Society.

[76]  Kou-San Ju,et al.  Nitroaromatic Compounds, from Synthesis to Biodegradation , 2010, Microbiology and Molecular Biology Reviews.

[77]  S. W. Thomas,et al.  Chemical sensors based on amplifying fluorescent conjugated polymers. , 2007, Chemical reviews.

[78]  Giseop Kwak,et al.  Fluorescent Actuator Based on Microporous Conjugated Polymer with Intramolecular Stack Structure , 2012, Advanced materials.

[79]  G. Rothenberg,et al.  Dual-mode humidity detection using a lanthanide-based metal-organic framework: towards multifunctional humidity sensors. , 2017, Chemical communications.

[80]  Lars Öhrström,et al.  Terminology of metal–organic frameworks and coordination polymers (IUPAC Recommendations 2013) , 2013 .

[81]  Gregory S. Day,et al.  Luminescent sensors based on metal-organic frameworks , 2018 .

[82]  G. Choppin,et al.  Applications of lanthanide luminescence spectroscopy to solution studies of coordination chemistry , 1998 .

[83]  Dongpeng Yan,et al.  Long-afterglow metal–organic frameworks: reversible guest-induced phosphorescence tunability , 2016, Chemical science.

[84]  M. Costa,et al.  Toxicity and carcinogenicity of Cr(VI) in animal models and humans. , 1997, Critical reviews in toxicology.

[85]  Qin Zhou,et al.  Fluorescent Chemosensors Based on Energy Migration in Conjugated Polymers: The Molecular Wire Approach to Increased Sensitivity , 1995 .

[86]  Zhiyu Wang,et al.  Confinement of pyridinium hemicyanine dye within an anionic metal-organic framework for two-photon-pumped lasing , 2013, Nature Communications.

[87]  G. Shimizu,et al.  Alkaline-earth phosphonate MOFs with reversible hydration-dependent fluorescence. , 2016, Chemical communications.

[88]  Guangtao Li,et al.  Dye@bio-MOF-1 Composite as a Dual-Emitting Platform for Enhanced Detection of a Wide Range of Explosive Molecules. , 2017, ACS applied materials & interfaces.

[89]  Ayalew H. Assen,et al.  Ultra-Tuning of the Rare-Earth fcu-MOF Aperture Size for Selective Molecular Exclusion of Branched Paraffins. , 2015, Angewandte Chemie.

[90]  M. Allendorf,et al.  An updated roadmap for the integration of metal-organic frameworks with electronic devices and chemical sensors. , 2017, Chemical Society reviews.

[91]  Dan Zhao,et al.  Tuning the topology and functionality of metal-organic frameworks by ligand design. , 2011, Accounts of chemical research.

[92]  A. Douhal,et al.  Photochemistry of Zr-based MOFs: ligand-to-cluster charge transfer, energy transfer and excimer formation, what else is there? , 2016, Physical chemistry chemical physics : PCCP.

[93]  G. Collet,et al.  Lanthanide near infrared imaging in living cells with Yb3+ nano metal organic frameworks , 2013, Proceedings of the National Academy of Sciences.

[94]  Amilra Prasanna de Silva Luminescent Photoinduced Electron Transfer (PET) Molecules for Sensing and Logic Operations , 2011 .

[95]  M. Allendorf,et al.  Luminescent metal-organic frameworks. , 2009, Chemical Society reviews.

[96]  R. Navarro,et al.  Photodynamics of Zr-based MOFs: effect of explosive nitroaromatics. , 2017, Physical chemistry chemical physics : PCCP.

[97]  V. Balzani,et al.  Photochemistry and Photophysics: Concepts, Research, Applications , 2014 .

[98]  Jun Liang,et al.  Multifunctional metal-organic framework catalysts: synergistic catalysis and tandem reactions. , 2017, Chemical Society reviews.

[99]  Demin Liu,et al.  Nanoscale metal-organic frameworks for biomedical imaging and drug delivery. , 2011, Accounts of chemical research.

[100]  F. Chen,et al.  Host-guest interaction dictated selective adsorption and fluorescence quenching of a luminescent lightweight metal-organic framework toward liquid explosives. , 2014, Dalton Transactions.

[101]  B. Yan,et al.  Fabrication and application of a ratiometric and colorimetric fluorescent probe for Hg2+ based on dual-emissive metal–organic framework hybrids with carbon dots and Eu3+ , 2016 .

[102]  C. Pinel,et al.  Metal-organic frameworks: opportunities for catalysis. , 2009, Angewandte Chemie.

[103]  D. L. Dexter A Theory of Sensitized Luminescence in Solids , 1953 .

[104]  Stavros A. Diamantis,et al.  All in one porous material: Exceptional sorption and selective sensing of hexavalent chromium by using a Zr4+ MOF , 2017 .

[105]  S. Tanase,et al.  Ferrimagnetic Heisenberg chains derived from [M(CN)8]3- (M=Mo(V), W(V)) building-blocks. , 2008, Chemphyschem : a European journal of chemical physics and physical chemistry.

[106]  F. Bǎnicǎ,et al.  Chemical sensors and biosensors : fundamentals and applications , 2012 .

[107]  Chunying Duan,et al.  Metal–Organic Frameworks: Versatile Materials for Heterogeneous Photocatalysis , 2016 .

[108]  B. Ding,et al.  A unique multi-functional cationic luminescent metal–organic nanotube for highly sensitive detection of dichromate and selective high capacity adsorption of Congo red , 2016 .