Stereodifferentiation in the photochemical cycloreversion of diastereomeric methoxynaphthalene-oxetane dyads

[structure: see text] Intramolecular PET cycloreversion of oxetanes 1 and 2 has been achieved in acetonitrile and chloroform as solvents. Interestingly, a higher photoreactivity has been found in acetonitrile, while a significant stereodifferentiation has been found in chloroform. This stereodifferentiation can be attributed to the folded conformation which predominates in 2, with the naphthalene ring directed toward the oxetane region, allowing for the intramolecular electron transfer. Accordingly, intramolecular fluorescence quenching is also more efficient in acetonitrile, whereas stereodifferentiation is markedly higher in chloroform. Thus, a good correlation can be established between the results from steady-state irradiations and fluorescence measurements.     

A Reversible Dual‐Response Fluorescence Switch for the Detection of Multiple Analytes

This paper reports a reversible dual fluorescence switch for the detection of a proton target and 2,4,6‐trinitrotoluene (TNT) with opposite‐response results, based on fluorophore derivatization of silica nanoparticles. Fluorescent silica nanoparticles were synthesized through modification of the surface with a nitrobenzoxadiazole (NBD) fluorophore and an organic amine to form a hybrid monolayer of fluorophores and amino ligands; the resultant nanoparticles showed different fluorescence responses to the proton target and TNT. Protonation of the amino ligands leads to fluorescence enhancement due to inhibition of photoinduced electron transfer (PET) between the amine and fluorophore. By contrast, addition of TNT results in fluorescence quenching because a fluorescence resonance energy transfer (FRET) happens between the NBD fluorophore and the formed TNT–amine complex. The fluorescence signal is reversible through washing with the proper solvents and the nanoparticles can be reused after centrifugal separation. Furthermore, these nanoparticles were assembled into chips on an etched silicon wafer for the detection of TNT and the proton target. The assembled chip can be used as a convenient indicator of herbicide (2,4‐dichlorophenoxyacetic acid) and TNT residues with the use of only 10 μL of sample. The simple NBD‐grafted silica nanoparticles reported here show a reversible signal and good assembly flexibility; thus, they can be applied in multianalyte detection.     

2-萘-(OCH2CH2)n-金刚胺与6-单取代环糊精衍生物的光诱导电子转移反应

A number of naphthalene donor compounds that possess an adamantanamine binding moiety and an (OCH2CH2)n (nn1, 2, 3, 4, 6, 8) spacer were synthesized. The fluorescence quenching between these donor substrates and mono-6-O-p-nitrobenzoyl-β-cyclodextrin (pNBCD) and mono-6-O-m-nitrobenzoyl-β-cyclodextrin(mNBCD) was studied in detail. It was found that very efficient fluorescence quenching could occur in these supramolecular systems. This quenching was attributed to the photoinduced electron transfer inside the supramolecular assembly between the naphthalene donors and cyclodextrin acceptors. Detailed Stern-Volmer constants were measured and they were partitioned into dynamic Stern-Volmer quenching constants and static binding constants. It was demonstrated that the binding constants between all the naphthalene compounds and cyclodextrins are the same as they possess the same binding site, i.e., adamantanamine.     

Supramolecular Architectures by Fullerene‐Bridged Bis(permethyl‐β‐cyclodextrin)s with Porphyrins

The Hirsch–Bingel reaction of bis{4‐methyl[1,2,3]triazolyl}malonic ester‐bridged bis(permethyl‐β‐cyclodextrin) 1 with C₆₀ has led to the formation of a new fullerene‐bridged bis(permethyl‐β‐cyclodextrin) 2 , which has been comprehensively characterized by NMR spectroscopy, MALDI‐MS, and elemental analysis. Taking advantage of the high affinity between 2 and 5,10,15,20‐tetrakis(4‐sulfonatophenyl)porphyrin ( 3 ) or [5,10,15,20‐tetrakis(4‐sulfonatophenyl)porphinato]zinc(II) ( 4 ), linear supramolecular architectures with a width of about 2 nm and a length ranging from hundreds of nanometers to micron dimension were conveniently constructed and fully investigated by transmission electron microscopy (TEM), atomic force microscopy (AFM), and scanning electron microscopy (SEM). Significantly, the photoinduced electron‐transfer (PET) process between porphyrin and C₆₀ moieties takes place within the 2 ? 3 and 2 ? 4 supramolecular architectures under light irradiation, leading to the highly efficient quenching of the porphyrin fluorescence. The PET process and the charge‐separated state were investigated by means of fluorescence spectroscopy, fluorescence decay, cyclic voltammetry, and nanosecond transient absorption measurements.     

Tuning the photophysical behavior of luminescent cyclam derivatives by cation binding and excited state redox potential

The emission from two photoactive 14-membered macrocyclic ligands, 6-((naphthalen-1-ylmethyl)-amino)-trans-6,13-dimethyl-13-amino-1,4,8,11-tetraaza-cyclotetradecane (L1) and 6-((anthracen-9-ylmethyl)-amino)-trans-6,13-dimethyl-13-amino-1,4,8,11-tetraaza-cyclotetradecane (L2) is strongly quenched by a photoinduced electron transfer (PET) mechanism involving amine lone pairs as electron donors. Time-correlated single photon counting (TCSPC), multiplex transient grating (TG), and fluorescence upconversion (FU) measurements were performed to characterize this quenching mechanism. Upon complexation with the redox inactive metal ion, Zn(II), the emission of the ligands is dramatically altered, with a significant increase in the fluorescence quantum yields due to coordination-induced deactivation of the macrocyclic amine lone pair electron donors. For [ZnL2]2+, the substituted exocyclic amine nitrogen, which is not coordinated to the metal ion, does not quench the fluorescence due to an inductive effect of the proximal divalent metal ion that raises the ionization potential. However, for [ZnL1]2+, the naphthalene chromophore is a sufficiently strong excited-state oxidant for PET quenching to occur.     

Test‐Strip‐Based Fluorometric Detection of Fluoride in Aqueous Media with a BODIPY‐Linked Hydrogen‐Bonding Receptor

The measurement of biologically relevant anions, such as fluoride, is an important task in analytical chemistry, in particular, for dental health and osteoporosis. Although a large number of fluoride probes are known, the applicability under relevant conditions is limited to a few examples. To improve this situation, BODIPY‐amidothiourea dyes with varying hydrogen‐bond donating strengths were developed, the most H‐acidic of which ( 1 c ) could detect F^? from an inorganic source (NaF) in 50 % aqueous solution (DMSO/water 1:1, v/v) with 0.01 ppm sensitivity through selective fluorescence quenching by a photoinduced electron‐transfer (PET) process. Use of the probe and a reference dye with a test‐strip assay and a portable and rapidly recording lateral‐flow fluorescence reader made determination of F^? in neat aqueous solutions, such as spiked water samples and toothpaste extracts, possible in a self‐referenced manner, achieving a detection limit of 0.2 ppm.     

Fluorescence Quenching of Poly[2-methoxy-5-（2′-ethylhexoxy）-p-phenylene vinylene] （MEH-PPV） in Solutions

Fluorescence quenching processes of poly[2-methoxy-5-(2‘ethyl-hexoxy)-p-phenylene vinylene] (MEH-PPV) in solution by electron acceptors, O2 and acid, have been studied. Static quenching of the fluorescence from MEH-PPV by an electron acceptor (DDQ or TCNE) occurs due to electron transfer from MEH-PPV to the electron acceptor and this electron transfer quenching can be promoted by chloroform. Photooxidation takes place in the MEH-PPV solution and singlet oxygen is an intermediate in the photooxidation, according to the results of ESR spectroscopy. Acid also plays an important role in the fluorescence quenching process of MEH-PPV, by the protonation of the alkoxy groups in the molecular chain.     

Highly Efficient Singlet–Singlet Energy Transfer in Light‐Harvesting [60,70]Fullerene–4‐Amino‐1,8‐naphthalimide Dyads

New C₆₀ and C₇₀ fullerene dyads formed with 4‐amino‐1,8‐naphthalimide chromophores have been prepared by the Bingel cyclopropanation reaction. The resulting monoadducts were investigated with respect to their fluorescence properties (quantum yields and lifetimes) to unravel the role of the charge‐transfer naphthalimide chromophore as a light‐absorbing antenna and excited‐singlet‐state sensitizer of fullerenes. The underlying intramolecular singlet–singlet energy transfer (EnT) process was fully characterized and found to proceed quantitatively (Φ_EnT≈1) for all dyads. Thus, these conjugates are of considerable interest for applications in which fullerene excited states have to be created and photonic energy loss should be minimized. In polar solvents (tetrahydrofuran and benzonitrile), fluorescence quenching of the fullerene by electron transfer from the ground‐state aminonaphthalimide was postulated as an additional path.     

Coumarin‐3‐Aldehyde as a Scaffold for the Design of Tunable PET‐Modulated Fluorescent Sensors for Neurotransmitters

NeuroSensor 521 (NS521) is a fluorescent sensor for primary‐amine neurotransmitters based on a platform that consists of an aryl moiety appended to position C4 of the coumarin‐3‐aldehyde scaffold. We demonstrate that sensors based on this platform behave as a directly linked donor–acceptor system that operates through an intramolecular acceptor‐excited photoinduced electron transfer (a‐PET) mechanism. To evaluate the PET process, a series of benzene‐ and thiophene‐substituted derivatives were prepared and the photophysical properties, binding affinities, and fluorescence responses toward glutamate, norepinephrine, and dopamine were determined. The calculated energy of the highest occupied molecular orbital (E_HOMO) of the pendant aryl substituents, along with oxidation and reduction potential values derived from the calculated molecular orbital energy values of the platform components, allowed for calculation of the fluorescence properties of the benzene sensor series. Interestingly, the thiophene derivatives did not fit the typical PET model, highlighting the limitations of the method. A new sensor, NeuroSensor 539, displayed enhanced photophysical properties aptly suited for biological imaging. NeuroSensor 539 was validated by selectively labeling and imaging norepinephrine in secretory vesicles of live chromaffin cells.     

Pyrromethene derivatives in three‐component photoinitiating systems for free radical photopolymerization

1,3,5,7,8‐pentamethyl pyrromethene difluoroborate complex (HMP) and 2,6‐diethyl‐8‐phenyl‐1,3,5,7‐tetramethylpyrromethene difluoroborate complex (EPP) were used to initiate the polymerization of a diacrylate in a two‐ and a three‐component photoinitiating system (PIS), together with an amine (ethyl‐4‐dimethylaminobenzoate, EDB) and triazine A (2‐(4‐methoxyphenyl)‐4,6‐bis(trichloromethyl)‐1,3,5‐triazine, TA) as coinitiators. For both pyrromethene dyes, the highest conversion was achieved with the three‐component PIS. As these dyes have high‐fluorescence quantum yields, steady state and time‐resolved techniques were used to study the possible fluorescence quenching by the amine and the triazine, as well as laser flash photolysis to investigate the electron transfer process that occurs in these PIS from either the singlet or triplet excited states. The electron transfer reaction is evidenced by using time‐resolved photoconductivity. Experiments show that the main interaction between the dye and both coinitiators is through its excited singlet state and the process is more efficient when TA is present. The beneficial effect noted when both coinitiators are used in a three‐component system is ascribed to secondary reactions between the coinitiators and intermediates that lead to the generation of higher amount of initiating species and the recovery of the initial dye. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 48: 2594–2603, 2010     

Nondestructive Photoluminescence Read‐Out by Intramolecular Electron Transfer in a Perylene Bisimide‐Diarylethene Dyad

A novel, highly stable photochromic dyad 3 based on a perylene bisimide (PBI) fluorophore and a diarylethene (DAE) photochrome was synthesized and the optical and photophysical properties of this dyad were studied in detail by steady‐state and time‐resolved ultrafast spectroscopy. This photochromic dyad can be switched reversibly by UV‐light irradiation of its ring‐open form 3 o leading to the ring‐closed form 3 c , and back reaction of 3 c to 3 o by irradiation with visible light. Solvent‐dependent fluorescence studies revealed that the emission of ring‐closed form 3 c is drastically quenched in solvents of medium (e.g., chloroform) to high (e.g., acetone) polarities, while the emission of the ring‐open form 3 o is appreciably quenched only in highly polar solvents like DMF. The strong fluorescence quenching of 3 c is attributed to a photoinduced electron‐transfer (PET) process from the excited PBI unit to ring‐closed DAE moiety, as this process is thermodynamically highly favorable with a Gibbs free energy value of ?0.34 eV in dichloromethane. The electron‐transfer mechanism for the fluorescence quenching of ring‐closed 3 c is substantiated by ultrafast transient measurements in dichloromethane and acetone, revealing stabilization of charge‐separated states of 3 c in these solvents. Our results reported here show that the new photochromic dyad 3 has potential for nondestructive read‐out in write/read/erase fluorescent memory systems.     

Comparative photophysical behaviour of naphthalene-linked crown ethers and aza crown ethers of varying cavity dimensions

A comparative time-resolved emission studies of several naphtho-crown ethers I–V, where metal ions can be complexed in a predetermined orientation with respect to the naphthalene (Naph) π-plane and naphthalene-linked aza crown ethers (L1 and L2) have been presented. In both the systems, crown ethers and aza crown ethers, naphthalene fluorescence gets quenched. In the systems I to V, the quenching is mainly due to efficient spin-orbit coupling (SOC) leading to greater population of the lowest triplet state of naphthalene. This SOC depends on the orientation of the crown ring with respect to the Naph-π-plane. However, in the systems L1 and L2, the quenching is due to photoinduced electron transfer (PET) from nitrogen lone pair of the aza crown ring to naphthalene moiety and consequent exciplex formation. The results have been interpreted using the time-resolved emission studies of all the compounds in various solvents, their alkali metal ion complexes, and protonated ligands.     

Aptamer‐Based Turn‐On Detection of Thrombin in Biological Fluids Based on Efficient Phosphorescence Energy Transfer from Mn‐Doped ZnS Quantum Dots to Carbon Nanodots

This paper presents the first example of a sensitive, selective, and stable phosphorescent sensor based on phosphorescence energy transfer (PET) for thrombin that functions through thrombin–aptamer recognition events. In this work, an efficient PET donor–acceptor pair using Mn‐doped ZnS quantum dots labeled with thrombin‐binding aptamers (TBA QDs) as donors, and carbon nanodots (CNDs) as acceptors has been constructed. Due to the π–π stacking interaction between aptamer and CNDs, the energy donor and acceptor are taken into close proximity, leading to the phosphorescence quenching of donors, TBA QDs. A maximum phosphorescence quenching efficiency as high as 95.9 % is acquired. With the introduction of thrombin to the “off state” of the TBA‐QDs‐CNDs system, the phosphorescence is “turned on” due to the formation of quadruplex‐thrombin complexes, which releases the energy acceptor CNDs from the energy donors. Based on the restored phosphorescence, an aptamer‐based turn‐on thrombin biosensor has been demonstrated by using the phosphorescence as a signal transduction method. The sensor displays a linear range of 0–40 nM for thrombin, with a detection limit as low as 0.013 nM in pure buffers. The proposed aptasensor has also been used to monitor thrombin in complex biological fluids, including serum and plasma, with satisfactory recovery ranging from 96.8 to 104.3 %. This is the first time that Mn‐doped ZnS quantum dots and CNDs have been employed as a donor–acceptor pair to construct PET‐based biosensors, which combines both the photophysical merits of phosphorescence QDs and the superquenching ability of CNDs and thus affords excellent analytical performance. We believe this proposed method could pave the way to a new design of biosensors using PET systems.     

Sensing of 2,4,6‐Trinitrotoluene (TNT) and 2,4‐Dinitrotoluene (2,4‐DNT) in the Solid State with Photoluminescent RuII and IrIII Complexes

A series of metal–organic chromophores containing Ru^II or Ir^III were studied for the luminometric detection of nitroaromatic compounds, including trinitrotoluene (TNT). These complexes display long‐lived, intense photoluminescence in the visible region and are demonstrated to serve as luminescent sensors for nitroaromatics. The solution‐based behavior of these photoluminescent molecules has been studied in detail in order to identify the mechanism responsible for metal‐to‐ligand charge‐transfer (MLCT) excited state quenching upon addition of TNT and 2,4‐dinitrotoluene (2,4‐DNT). A combination of static and dynamic spectroscopic measurements unequivocally confirmed that the quenching was due to a photoinduced electron transfer (PET) process. Ultrafast transient absorption experiments confirmed the formation of the TNT radical anion product following excited state electron transfer from these metal complexes. Reported for the first time, photoluminescence quenching realized through ink‐jet printing and solid‐state titrations was used for the solid‐state detection of TNT; achieving a limit‐of‐quantitation (LOQ) as low as 5.6 ng cm^?2. The combined effect of a long‐lived excited state and an energetically favorable driving force for the PET process makes the Ru^II and Ir^III MLCT complexes discussed here particularly appealing for the detection of nitroaromatic volatiles and related high‐energy compounds.     

A mechanistic investigation of a three‐component radical photoinitiator system comprising methylene blue,N‐methyldiethanolamine,and diphenyliodonium chloride

Three‐component systems, which contain a light‐absorbing species (typically a dye), an electron donor (typically an amine), and a third component (usually an iodonium salt), have emerged as efficient, visible‐light‐sensitive photoinitiators. Although three‐component systems have been consistently found to be faster and more efficient than their two‐component counterparts, these systems are not well understood and a number of distinct mechanisms have been reported in the literature. In this contribution, photodifferential scanning calorimetry and in situ, time‐resolved, laser‐induced, steady‐state fluorescence spectroscopy were used to study the initiation mechanism of the three‐component system methylene blue, N‐methyldiethanolamine and diphenyliodonium chloride. Kinetic studies based upon photodifferential scanning calorimetry reveal a significant increase in polymerization rate with increasing concentration of either the amine or the iodonium salt. However, the laser‐induced fluorescence experiments show that while increasing the amine concentration dramatically increases the rate of dye fluorescence decay, increasing the DPI concentration actually slows consumption of the dye. We concluded that the primary photochemical reaction involves electron transfer from the amine to the dye. We suggest that the iodonium salt reacts with the resulting dye‐based radical (which is active only for termination) to regenerate the original dye and simultaneously produce a phenyl radical (active in initiation) derived from the diphenyliodonium salt. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2057–2066, 2000     

Coronenetetraimide‐Centered Cruciform Pentamers Containing Multiporphyrin Units: Synthesis and Sequential Photoinduced Energy‐ and Electron‐Transfer Dynamics

A series of coronenetetraimide (CorTIm)‐centered cruciform pentamers containing multiporphyrin units, in which four porphyrin units are covalently linked to a CorTIm core through benzyl linkages, were designed and synthesized to investigate their structural, spectroscopic, and electrochemical properties as well as photoinduced electron‐ and energy‐transfer dynamics. These systems afforded the first synthetic case of coroneneimide derivatives covalently linked with dye molecules. The steady‐state absorption and electrochemical results indicate that a CorTIm and four porphyrin units were successfully characterized by the corresponding reference monomers. In contrast, the steady‐state fluorescence measurements demonstrated that strong fluorescence quenching relative to the corresponding monomer units was observed in these pentamers. Nanosecond laser flash photolysis measurements revealed the occurrence of intermolecular electron transfer from triplet excited state of zinc porphyrins to CorTIm. Femtosecond laser‐induced transient absorption measurements for excitation of the CorTIm unit clearly demonstrate the sequential photoinduced energy and electron transfer between CorTIm and porphyrins, that is, occurrence of the initial energy transfer from CorTIm (energy donor) to porphyrins (energy acceptor) and subsequent electron transfer from porphyrins (electron donor) to CorTIm (electron acceptor) in these pentamers, whereas only the electron‐transfer process from porphyrins to CorTIm was observed when we mainly excite porphyrin units. Finally, construction of high‐order supramolecular patterning of these pentamers was performed by utilizing self‐assembly and physical dewetting during the evaporation of solvent.     

Photoinduced Electron Transfer in Host-Guest Complexes of 2-Naphthyl-O(CH2) n -adamantanamines with Mono-6-O-p-nitrobenzoyl-β-cyclodextrin and Mono-6-O-m-nitrobenzoyl-β-cyclodextrin

A number of naphthalene derivatives containing adamantanamine binding moiety and an (CH₂) _n (n=2, 3, 4, 5, 6) spacer were prepared as the electron donor. A supramolecular assembly was fabricated by the inclusion between the donor substrates and the host molecules, i.e., mono-6-O-p-nitrobenzoyl-β-cyclodextrin (pNBCD) and mono-6-O-m-nitrobenzoyl-β-cyclodextrin (mNBCD), in water. The fluorescence quenching in these systems was studied in detail. It revealed efficient photoinduced electron transfers (PET) between the naphthalene donors and the cyclodextrin acceptors. This PET process was partitioned into a dynamic quenching component caused by bimolecule collision reactions and a static quenching component due to hydrophobic binding between the donor and acceptor molecules. Detailed Stern–Volmer constants were measured and they were partitioned into dynamic Stern–Volmer quenching constants (dynamic quenching) and static binding constants (static quenching). In these two pathways, the static quenching was found to be highly efficient and dominant in the presence of NBCD.     

Diels–Alder Polymer Networks with Temperature‐Reversible Cross‐Linking‐Induced Emission

A novel synthetic strategy gives reversible cross‐linked polymeric materials with tunable fluorescence properties. Dimaleimide‐substituted tetraphenylethene (TPE‐2MI), which is non‐emissive owing to the photo‐induced electron transfer (PET) between maleimide (MI) and tetraphenylethene (TPE) groups, was used to cross‐link random copolymers of methyl (MM), decyl (DM) or lauryl (LM) methacrylate with furfuryl methacrylate (FM). The mixture of copolymer and TPE‐2MI in DMF showed reversible fluorescence with “on/off” behavior depending on the Diels–Alder (DA)/retro‐DA process, which is easily adjusted by temperature. At high temperatures, the retro‐DA reaction is dominant, and the fluorescence is quenched by the photo‐induced electron transfer (PET) mechanism. In contrast, at low temperatures, the emission recovers as the DA reaction takes over. A transparent PMFM/TPE‐2MI polymer film was prepared which shows an accurate response to the external temperature and exhibited tunable fluorescent “turn on/off” behavior. These results suggest the possible application in areas including information security and transmission. An example of invisible/visible writing is given.     

On the Role of Hydrogen Bonds in Photoinduced Electron‐Transfer Dynamics between 9‐Fluorenone and Amine Solvents

Using ultrafast fluorescence upconversion and mid‐infrared spectroscopy, we explore the role of hydrogen bonds in the photoinduced electron transfer (ET) between 9‐fluorenone (FLU) and the solvents trimethylamine (TEA) and dimethylamine (DEA). FLU shows hydrogen‐bond dynamics in the methanol solvent upon photoexcitation, and similar effects may be anticipated when using DEA, whereas no hydrogen bonds can occur in TEA. Photoexcitation of the electron‐acceptor dye molecule FLU with a 400 nm pump pulse induces ultrafast ET from the amine solvents, which is followed by 100 fs IR probe pulses as well as fluorescence upconversion, monitoring the time evolution of marker bands of the FLU S₁ state and the FLU radical anion, and an overtone band of the amine solvent, marking the transient generation of the amine radical cation. A comparison of the experimentally determined forward charge‐separation and backward charge‐recombination rates for the FLU‐TEA and FLU‐DEA reaction systems with the driving‐force dependencies calculated for the forward and backward ET rates reveals that additional degrees of freedom determine the ET reaction dynamics for the FLU‐DEA system. We suggest that hydrogen bonding between the DEA molecules plays a key role in this behaviour.     

Integration of the 1,2,3‐Triazole “Click” Motif as a Potent Signalling Element in Metal Ion Responsive Fluorescent Probes

In a systematic approach we synthesized a new series of fluorescent probes incorporating donor–acceptor (D‐A) substituted 1,2,3‐triazoles as conjugative π‐linkers between the alkali metal ion receptor N‐phenylaza‐[18]crown‐6 and different fluorophoric groups with different electron‐acceptor properties (4‐naphthalimide, meso‐phenyl‐BODIPY and 9‐anthracene) and investigated their performance in organic and aqueous environments (physiological conditions). In the charge‐transfer (CT) type probes 1 , 2 and 7 , the fluorescence is almost completely quenched by intramolecular CT (ICT) processes involving charge‐separated states. In the presence of Na⁺ and K⁺ ICT is interrupted, which resulted in a lighting‐up of the fluorescence in acetonitrile. Among the investigated fluoroionophores, compound 7 , which contains a 9‐anthracenyl moiety as the electron‐accepting fluorophore, is the only probe which retains light‐up features in water and works as a highly K⁺/Na⁺‐selective probe under simulated physiological conditions. Virtually decoupled BODIPY‐based 6 and photoinduced electron transfer (PET) type probes 3 – 5 , where the 10‐substituted anthracen‐9‐yl fluorophores are connected to the 1,2,3‐triazole through a methylene spacer, show strong ion‐induced fluorescence enhancement in acetonitrile, but not under physiological conditions. Electrochemical studies and theoretical calculations were used to assess and support the underlying mechanisms for the new ICT and PET 1,2,3‐triazole fluoroionophores.