Fluorescent Aromatic Tag-Functionalized MOFs for Highly Selective Sensing of Metal Ions and Small Organic Molecules.

By varying the fluorescent tags of resorcin[4]arene-based tetracarboxylic acids from phenyl to naphthyl, two highly luminescent metal-organic frameworks (MOFs), namely, [Zn2(TPC4A)(DMF)(H2O)4]·3H2O (1) and [(CH3)2NH2]2[Zn(TNC4A)]·4H2O (2), were successfully achieved (TPC4A = 2,8,14,20-tetra-phenyl-6,12,18,24-tetra-methoxy-4,10,16,22-tetra-carboxy-methoxy-resorcin[4]arene and TNC4A = 2,8,14,20-tetra-1-naphthal-6,12,18,24-tetra- methoxy-4,10,16,22-tetra-carboxy-methoxy-resorcin[4]arene). Compound 1 features a unique 2D network, while 2 exhibits a fascinating 3D framework. The highly selective detection of small organic molecules as well as Fe(2+) and Fe(3+) was performed for 1 and 2 as fluorescent sensors. Remarkably, luminescent 1 and 2 were used as sensory materials for the sensing of various amine vapors with high selectivity and rapid response. Most strikingly, clear fluorescence "on-off" switch-functions toward small organic molecules as well as amine vapors were also explored for luminescent 1 and 2.

[1]  Hua Wu,et al.  An unprecedented 2D → 3D metal-organic polyrotaxane framework constructed from cadmium and a flexible star-like ligand. , 2011, Chemical communications.

[2]  Di Sun,et al.  A tubular europium-organic framework exhibiting selective sensing of Fe3+ and Al3+ over mixed metal ions. , 2013, Chemical communications.

[3]  Z. Su,et al.  Pillared metal organic frameworks for the luminescence sensing of small molecules and metal ions in aqueous solutions. , 2015, Dalton transactions.

[4]  K. Saitow,et al.  Enhancement of fluorescence intensity by silicon particles and its size effect. , 2014, Chemical communications.

[5]  O. Wolfbeis,et al.  Quenching of the luminescence of upconverting luminescent nanoparticles by heavy metal ions. , 2011, Chemistry.

[6]  M. Allendorf,et al.  Influence of connectivity and porosity on ligand-based luminescence in zinc metal-organic frameworks. , 2007, Journal of the American Chemical Society.

[7]  Vânia F. Pais,et al.  OFF-ON-OFF Fluorescence Switch with T-Latch Function , 2011, Organic letters.

[8]  Qiang Zhao,et al.  Rational design of an "OFF-ON" phosphorescent chemodosimeter based on an iridium(III) complex and its application for time-resolved luminescent detection and bioimaging of cysteine and homocysteine. , 2013, Chemistry.

[9]  F. Nastasi,et al.  Solid-state luminescence switching of platinum(ii) dithiooxamide complexes in the presence of hydrogen halide and amine gases. , 2007, Chemical communications.

[10]  Sebastian Reineke,et al.  Selective turn-on ammonia sensing enabled by high-temperature fluorescence in metal-organic frameworks with open metal sites. , 2013, Journal of the American Chemical Society.

[11]  B. Yan,et al.  Eu(III)-functionalized MIL-124 as fluorescent probe for highly selectively sensing ions and organic small molecules especially for Fe(III) and Fe(II). , 2015, ACS applied materials & interfaces.

[12]  K. Ohkubo,et al.  Fluorescent zinc sensor with minimized proton-induced interferences: photophysical mechanism for fluorescence turn-on response and detection of endogenous free zinc ions. , 2012, Inorganic chemistry.

[13]  Hengwei Lin,et al.  Preoxidation for colorimetric sensor array detection of VOCs. , 2011, Journal of the American Chemical Society.

[14]  P. Chou,et al.  Diphenyl(1-naphthyl)phosphine ancillary for assembling of red and orange-emitting Ir(III) based phosphors; strategic synthesis, photophysics, and organic light-emitting diode fabrication. , 2010, Inorganic chemistry.

[15]  Jin Yang,et al.  Two heterometallic-organic frameworks composed of iron(III)-salen-based ligands and d(10) metals: gas sorption and visible-light photocatalytic degradation of 2-chlorophenol. , 2015, Chemistry.

[16]  Jong Seung Kim,et al.  Naphthalimide Trifluoroacetyl Acetonate: A Hydrazine-Selective Chemodosimetric Sensor , 2013 .

[17]  J. Pablos,et al.  Solid polymer substrates and coated fibers containing 2,4,6-trinitrobenzene motifs as smart labels for the visual detection of biogenic amine vapors. , 2015, Chemistry.

[18]  Bettina V. Lotsch,et al.  Tandem MOF-Based Photonic Crystals for Enhanced Analyte-Specific Optical Detection , 2015 .

[19]  C. Zheng,et al.  A systematic study of fluorescence-based detection of nitroexplosives and other aromatics in the vapor phase by microporous metal-organic frameworks. , 2013, Chemistry.

[20]  Yun Wang,et al.  Controllable syntheses of porous metal-organic frameworks: encapsulation of Ln(III) cations for tunable luminescence and small drug molecules for efficient delivery. , 2013, Chemistry.

[21]  L. Chi,et al.  Ion‐Specific Aggregation of GoldDNA Nanoparticles Using the dG Quartet Hairpin 5′‐d(G4T4G4) , 2005, Chemistry & biodiversity.

[22]  Bing Yan,et al.  A novel fluorescence probe for sensing organic amine vapors from a Eu3+ β-diketonate functionalized bio-MOF-1 hybrid system , 2015 .

[23]  P. Cheng,et al.  Highly selective luminescent sensing of fluoride and organic small-molecule pollutants based on novel lanthanide metal-organic frameworks. , 2013, Inorganic chemistry.

[24]  Luís D. Carlos,et al.  Luminescent multifunctional lanthanides-based metal-organic frameworks. , 2011, Chemical Society reviews.

[25]  W. Nam,et al.  Cyclometalated iridium(III) complexes for phosphorescence sensing of biological metal ions. , 2014, Inorganic chemistry.

[26]  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.

[27]  Y. Li,et al.  Metal-organic framework MIL-101 as a low background signal platform for label-free DNA detection. , 2014, The Analyst.

[28]  Y. Inoue,et al.  First Synthesis, Isolation and Characterization of Enantiomerically Pure and Inherently Chiral Resorc[4]arenes by Lewis Acid Cyclization of a Resorcinol Monoalkyl Ether , 2003 .

[29]  Dawei Huang,et al.  Highly sensitive strategy for Hg2+ detection in environmental water samples using long lifetime fluorescence quantum dots and gold nanoparticles. , 2013, Environmental science & technology.

[30]  K. Kimura,et al.  Highly selective recognition of acetate and bicarbonate by thiourea-functionalised inverse opal hydrogel in aqueous solution. , 2013, Chemical communications.

[31]  R. Niessner,et al.  Determination of primary, secondary, and tertiary amines in air by direct or diffusion sampling followed by determination with liquid chromatography and tandem mass spectrometry. , 2008, Environmental science & technology.

[32]  Eric V. Anslyn,et al.  Array sensing using optical methods for detection of chemical and biological hazards. , 2013, Chemical Society reviews.

[33]  Xun Wang,et al.  Hierarchical Zn/Ni-MOF-2 nanosheet-assembled hollow nanocubes for multicomponent catalytic reactions. , 2014, Angewandte Chemie.

[34]  T. Hirayama,et al.  A highly selective turn-on fluorescent probe for iron(II) to visualize labile iron in living cells , 2013 .

[35]  Chao Zou,et al.  A luminescent dye@MOF platform: emission fingerprint relationships of volatile organic molecules. , 2014, Angewandte Chemie.

[36]  Jun-Hao Wang,et al.  A dynamic, luminescent and entangled MOF as a qualitative sensor for volatile organic solvents and a quantitative monitor for acetonitrile vapour , 2013 .

[37]  W. Frank,et al.  Microwave-assisted synthesis of water-soluble, fluorescent gold nanoclusters capped with small organic molecules and a revealing fluorescence and X-ray absorption study. , 2015, Nanoscale.

[38]  P. S. Subramanian,et al.  Lanthanide(III) complexes of bis-semicarbazone and bis-imine-substituted phenanthroline ligands: solid-state structures, photophysical properties, and anion sensing. , 2012, Chemistry.

[39]  Rui Wang,et al.  Highly selective Fe3+ sensing and proton conduction in a water-stable sulfonate–carboxylate Tb–organic-framework , 2015 .

[40]  M. Mocerino,et al.  Pyridine-functionalised C4 symmetric resorcinarenes , 2007 .

[41]  M. Formica,et al.  New fluorescent chemosensors for metal ions in solution , 2012 .

[42]  Hong-Mei Zhang,et al.  Metal-ion exchange, small-molecule sensing, selective dye adsorption, and reversible iodine uptake of three coordination polymers constructed by a new resorcin[4]arene-based tetracarboxylate. , 2015, Inorganic chemistry.

[43]  Coordination polymers for energy transfer: Preparations, properties, sensing applications, and perspectives , 2015 .

[44]  I. Pinnau,et al.  Quest for anionic MOF membranes: continuous sod-ZMOF membrane with CO2 adsorption-driven selectivity. , 2015, Journal of the American Chemical Society.

[45]  Yanyan Fu,et al.  Turn on fluorescence sensing of vapor phase electron donating amines via tetraphenylporphyrin or metallophenylporphrin doped polyfluorene. , 2010, Chemical communications.

[46]  Paul T Anastas,et al.  Toward a comprehensive molecular design framework for reduced hazard. , 2010, Chemical reviews.

[47]  V. Staroverov,et al.  Effect of Extended π Conjugation on the Spectroscopic and Electrochemical Properties of Boron Difluoride Formazanate Complexes. , 2015, The Journal of organic chemistry.

[48]  Lena Freimuth,et al.  Bifunctional diaminoterephthalate scaffolds as fluorescence turn-on probes for thiols. , 2015, Chemistry.

[49]  J. Chinta,et al.  Calix[4]arene-based 1,3-diconjugate of salicylyl imine having dibenzyl amine moiety (L): synthesis, characterization, receptor properties toward Fe2+, Cu2+, and Zn2+, crystal structures of its Zn2+ and Cu2+ complexes, and selective phosphate sensing by the [ZnL]. , 2011, Inorganic chemistry.

[50]  Yanfeng Yue,et al.  Luminescent functional metal-organic frameworks. , 2012, Chemical Reviews.

[51]  P. Cheng,et al.  Experimental Studies and Mechanism Analysis of High-Sensitivity Luminescent Sensing of Pollutional Small Molecules and Ions in Ln4O4 Cluster Based Microporous Metal–Organic Frameworks , 2014 .

[52]  D. Cao,et al.  An amino group functionalized metal–organic framework as a luminescent probe for highly selective sensing of Fe3+ ions , 2014 .

[53]  Jianzhang Zhao,et al.  Tuning the emission properties of cyclometalated platinum(II) complexes by intramolecular electron-sink/arylethynylated ligands and its application for enhanced luminescent oxygen sensing , 2010 .

[54]  Jin Yang,et al.  Series of 2D and 3D coordination polymers based on 1,2,3,4-benzenetetracarboxylate and N-donor ligands: synthesis, topological structures, and photoluminescent properties. , 2010, Inorganic chemistry.

[55]  A. J. Blake,et al.  Synthesis and coordination properties of quinoline pendant arm derivatives of [9]aneN(3) and [9]aneN(2)S as fluorescent zinc sensors. , 2009, Inorganic chemistry.

[56]  K. Heinze,et al.  Dual application of (aqua)(chlorido)(porphyrinato)chromium(III) as hypersensitive amine-triggered ON switch and for dioxygen activation. , 2014, Inorganic chemistry.

[57]  Soumya Mukherjee,et al.  Highly selective detection of nitro explosives by a luminescent metal-organic framework. , 2013, Angewandte Chemie.

[58]  Xiaofeng Ma,et al.  Optical chemosensors based on transmetalation of salen-based Schiff base complexes. , 2014, Inorganic chemistry.

[59]  Bin Zhao,et al.  Lanthanide organic framework as a regenerable luminescent probe for Fe(3+). , 2015, Inorganic chemistry.

[60]  T. Swager,et al.  Fluorescence sensing of amine vapors using a cationic conjugated polymer combined with various anions. , 2014, Angewandte Chemie.

[61]  G. Pang,et al.  Fast response and highly selective sensing of amine vapors using a luminescent coordination polymer. , 2014, Chemical communications.

[62]  Bin Zhao,et al.  Unique Chiral Interpenetrating d-f Heterometallic MOFs as Luminescent Sensors. , 2015, Inorganic chemistry.

[63]  G. Malandrino,et al.  Phase transition and vapochromism in molecular assemblies of a polymorphic zinc(II) Schiff-base complex. , 2014, Inorganic chemistry.

[64]  Zhong‐Ming Sun,et al.  Highly selective acetone fluorescent sensors based on microporous Cd(II) metal–organic frameworks , 2012 .

[65]  Anthony L. Spek,et al.  Journal of , 1993 .

[66]  Y. Lan,et al.  An ultrastable porous metal–organic framework luminescent switch towards aromatic compounds , 2015 .

[67]  Yong Huang,et al.  A dual-fluorescent composite of graphene oxide and poly(3-hexylthiophene) enables the ratiometric detection of amines , 2014 .

[68]  E. Farhi,et al.  An extremely radioresistant green eukaryote for radionuclide bio-decontamination in the nuclear industry , 2013 .

[69]  Yu Yang,et al.  Luminescent Open Metal Sites within a Metal–Organic Framework for Sensing Small Molecules , 2007 .

[70]  Yu Liu,et al.  Reversible and selective sensing of aniline vapor by perylene-bridged bis(cyclodextrins) assembly. , 2011, The Journal of organic chemistry.

[71]  G. Zhu,et al.  A porous metal–organic framework formed by a V-shaped ligand and Zn(II) ion with highly selective sensing for nitroaromatic explosives , 2015 .

[72]  Partha Mahata,et al.  Highly Selective and Sensitive Luminescence Turn-On-Based Sensing of Al(3+) Ions in Aqueous Medium Using a MOF with Free Functional Sites. , 2015, Inorganic chemistry.

[73]  H. Katz,et al.  Highly sensitive NH3 detection based on organic field-effect transistors with tris(pentafluorophenyl)borane as receptor. , 2012, Journal of the American Chemical Society.

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

[75]  Jincai Zhao,et al.  Fluorescent bilayer nanocoils assembled from an asymmetric perylene diimide molecule with ultrasensitivity for amine vapors. , 2014, Chemical communications.