Lanthanide MOFs for inducing molecular chirality of achiral stilbazolium with strong circularly polarized luminescence and efficient energy transfer for color tuning

We present herein an innovative host–guest method to achieve induced molecular chirality from an achiral stilbazolium dye (DSM). The host–guest system is exquisitely designed by encapsulating the dye molecule in the molecule-sized chiral channel of homochiral lanthanide metal–organic frameworks (P-(+)/M-(−)-TbBTC), in which the P- or M-configuration of the dye is unidirectionally generated via a spatial confinement effect of the MOF and solidified by the dangling water molecules in the channel. Induced chirality of DSM is characterized by solid-state circularly polarized luminescence (CPL) and micro-area polarized emission of DSM@TbTBC, both excited with 514 nm light. A luminescence dissymmetry factor of 10⁻³ is obtained and the photoluminescence quantum yield (PLQY) of the encapsulated DSM in DSM@TbTBC is ∼10%, which is close to the PLQY value of DSM in dilute dichloromethane. Color-tuning from green to red is achieved, owing to efficient energy transfer (up to 56%) from Ln³⁺ to the dye. Therefore, this study for the first time exhibits an elegant host–guest system that shows induced strong CPL emission and enables efficient energy transfer from the host chiral Ln-MOF to the achiral guest DSM with the emission color tuned from green to red.

Homochiral Ln-MOFs are synthesized to encapsulate achiral dyes to induce strong circularly polarized luminescence with a luminescence dissymmetry factor of 10⁻³.     

Triboluminescence of a new family of CuI–NHC complexes in crystalline solid and in amorphous polymer films

Triboluminescent compounds that generate emission of light in response to mechanical stimulus are promising targets in the development of “smart materials” and damage sensors. Among triboluminescent metal complexes, rare-earth europium and terbium complexes are most widely used, while there is no systematic data on more readily available and inexpensive Cu complexes. We report a new family of photoluminescent Cu–NHC complexes that show bright triboluminescence (TL) in the crystal state visible in ambient indoor light under air. Moreover, when these complexes are blended into amorphous polymer films even at small concentrations, TL is easily observed. Observation of TL in polymer films overcomes the limitation of using crystals and opens up possibilities for the development of mechanoresponsive coatings and materials based on inexpensive metals such as Cu. Our results may also have implications for the understanding of the TL effect''s origin in polymer films.

Triboluminescent compounds that generate emission of light in response to mechanical stimulus are promising targets in the development of “smart materials” and damage sensors.     

Advances in anion binding and sensing using luminescent lanthanide complexes

Luminescent lanthanide complexes have been actively studied as selective anion receptors for the past two decades. Ln(iii) complexes, particularly of europium(iii) and terbium(iii), offer unique photophysical properties that are very valuable for anion sensing in biological media, including long luminescence lifetimes (milliseconds) that enable time-gating methods to eliminate background autofluorescence from biomolecules, and line-like emission spectra that allow ratiometric measurements. By careful design of the organic ligand, stable Ln(iii) complexes can be devised for rapid and reversible anion binding, providing a luminescence response that is fast and sensitive, offering the high spatial resolution required for biological imaging applications. This review focuses on recent progress in the development of Ln(iii) receptors that exhibit sufficiently high anion selectivity to be utilised in biological or environmental sensing applications. We evaluate the mechanisms of anion binding and sensing, and the strategies employed to tune anion affinity and selectivity, through variations in the structure and geometry of the ligand. We highlight examples of luminescent Ln(iii) receptors that have been utilised to detect and quantify specific anions in biological media (e.g. human serum), monitor enzyme reactions in real-time, and visualise target anions with high sensitivity in living cells.

This minireview highlights advances in anion binding and sensing using luminescent lanthanide(iii) complexes.     

Damming an electronic energy reservoir: ion-regulated electronic energy shuttling in a [2]rotaxane

We demonstrate the first example of bidirectional reversible electronic energy transfer (REET) between the mechanically bonded components of a rotaxane. Our prototypical system was designed such that photoexcitation of a chromophore in the axle results in temporary storage of electronic energy in a quasi-isoenergetic “reservoir” chromophore in the macrocycle. Over time, the emissive state of the axle is repopulated from this reservoir, resulting in long-lived, delayed luminescence. Importantly, we show that cation binding in the cavity formed by the mechanical bond perturbs the axle chromophore energy levels, modulating the REET process, and ultimately providing a luminescence read-out of cation binding. Modulation of REET processes represents an unexplored mechanism in luminescent molecular sensor development.

Delayed emission due to reversible electronic energy transfer (REET) between chromophores in the axle and macrocycle components of a rotaxane is demonstrated. The REET process can be modulated by metal ion binding in the cavity of the rotaxane.     

Polariton-assisted manipulation of energy relaxation pathways: donor–acceptor role reversal in a tuneable microcavity

Resonant interaction between excitonic transitions of molecules and localized electromagnetic field allows the formation of hybrid light–matter polaritonic states. This hybridization of the light and the matter states has been shown to significantly alter the intrinsic properties of molecular ensembles placed inside the optical cavity. Here, we have observed strong coupling of excitonic transition in a pair of closely located organic dye molecules demonstrating an efficient donor-to-acceptor resonance energy transfer with the mode of a tuneable open-access cavity. Analysing the dependence of the relaxation pathways between energy states in this system on the cavity detuning, we have demonstrated that predominant strong coupling of the cavity photon to the exciton transition in the donor dye molecule can lead not only to an increase in the donor–acceptor energy transfer, but also to an energy shift large enough to cause inversion between the energy states of the acceptor and the mainly donor lower polariton energy state. Furthermore, we have shown that the polariton-assisted donor–acceptor chromophores'' role reversal or “carnival effect” not only changes the relative energy levels of the donor–acceptor pair, but also makes it possible to manipulate the energy flow in the systems with resonant dipole–dipole interaction and direct energy transfer from the acceptor to the mainly donor lower polariton state. Our experimental data are the first confirmation of the theoretically predicted possibility of polariton-assisted energy transfer reversal in FRET systems, thus paving the way to new avenues in FRET-imaging, remote-controlled chemistry, and all-optical switching.

Polariton-assisted donor–acceptor role reversal in resonant energy transfer between organic dyes tagged with the terminus of the closed oligonucleotide-based molecular beacon strongly coupled to electromagnetic modes of a tuneable microcavity.     

Purely organic light-harvesting phosphorescence energy transfer by β-cyclodextrin pseudorotaxane for mitochondria targeted imaging

A new type of purely organic light-harvesting phosphorescence energy transfer (PET) supramolecular assembly is constructed from 4-(4-bromophenyl)-pyridine modified β-cyclodextrin (CD-PY) as a donor, cucurbit[8]uril (CB[8]) as a mediator, rhodamine B (RhB) as an acceptor, and adamantane modified hyaluronic acid (HA-ADA) as a cancer cell targeting agent. Interestingly, the complexation of free CD-PY, which has no RTP emission in aqueous solution, with CB[8] results in the formation of CD-PY@CB[8] pseudorotaxane with an RTP emission at 510 nm. Then the addition of RhB leads to an efficient light-harvesting PET process with highly efficient energy transfer and an ultrahigh antenna effect (36.42) between CD-PY@CB[8] pseudorotaxane and RhB. Importantly, CD-PY@CB[8]@RhB assembles with HA-ADA into nanoparticles with further enhanced delayed emission at 590 nm. The nanoparticles could be successfully used for mitochondria targeted imaging in A549 cancer cells. This aqueous-state PET based on a supramolecular assembly strategy has potential application in delayed fluorescence cell imaging.

A new type of purely organic light-harvesting PET supramolecular assembly is constructed with efficient energy transfer and ultrahigh antenna effect. Moreover, the assembly could be used for mitochondria targeted imaging in A549 cancer cells.     

Bright luminescent lithium and magnesium carbene complexes

We report on the convenient synthesis of a CNC pincer ligand composed of carbazole and two mesoionic carbenes, as well as the corresponding lithium- and magnesium complexes. Mono-deprotonation affords a rare “naked” amide anion. In contrast to the proligand and its mono-deprotonated form, tri-deprotonated s-block complexes show bright luminescence, and their photophysical properties were therefore investigated by absorption- and luminescence spectroscopy. They reveal a quantum yield of 16% in solution at ambient temperature. Detailed quantum-chemical calculations assist in rationalizing the emissive properties based on an Intra-Ligand-Charge-Transfer (ILCT) between the carbazolido- and mesoionic carbene ligands. (Earth-)alkali metals prevent the distortion of the ligand following excitation and, thus, by avoiding non-radiative deactivation support bright luminescence.

Lithium- and magnesium complexes of a CNC pincer ligand composed of carbazole and two mesoionic carbenes are bright luminescent, because the metals prevent molecular distortions upon excitation.     

Controlling the structure and photophysics of fluorophore dimers using multiple cucurbit[8]uril clampings

A modular strategy has been employed to develop a new class of fluorescent molecules, which generates discrete, dimeric stacked fluorophores upon complexation with multiple cucurbit[8]uril macrocycles. The multiple constraints result in a “static” complex (remaining as a single entity for more than 30 ms) and facilitate fluorophore coupling in the ground state, showing a significant bathochromic shift in absorption and emission. This modular design is surprisingly applicable and flexible and has been validated through an investigation of nine different fluorophore cores ranging in size, shape, and geometric variation of their clamping modules. All fluorescent dimers evaluated can be photo-excited to atypical excimer-like states with elongated excited lifetimes (up to 37 ns) and substantially high quantum yields (up to 1). This strategy offers a straightforward preparation of discrete fluorophore dimers, providing promising model systems with explicitly stable dimeric structures and tunable photophysical features, which can be utilized to study various intermolecular processes.

Dimerisation of a wide range of fluorophores through multiple CB[8] clampings leads to constrained intracomplex motion and distinct photophysical properties.     

Rational design of a “dual lock-and-key” supramolecular photosensitizer based on aromatic nucleophilic substitution for specific and enhanced photodynamic therapy

Photosensitizing agents are essential for precise and efficient photodynamic therapy (PDT). However, most of the conventional photosensitizers still suffer from limitations such as aggregation-caused quenching (ACQ) in physiological environments and toxic side-effects on normal tissues during treatment, leading to reduced therapeutic efficacy. Thus, integrating excellent photophysical properties and accurate carcinoma selectivity in a photosensitizer system remains highly desired. Herein, a “dual lock-and-key” supramolecular photosensitizer BIBCl–PAE NPs for specific and enhanced cancer therapy is reported. BIBCl–PAE NPs are constructed by encapsulating a rationally designed glutathione (GSH)-activatable photosensitizer BIBCl in a pH-responsive diblock copolymer. In normal tissues, BIBCl is “locked” in the hydrophobic core of the polymeric micelles due to ACQ. Under the “dual key” activation of low pH and high levels of GSH in a tumor microenvironment, the disassembly of micelles facilitates the reaction of BIBCl with GSH to release water-soluble BIBSG with ideal biocompatibility, enabling the highly efficient PDT. Moreover, benefiting from the Förster resonance energy transfer effect of BIBSG, improved light harvesting ability and ¹O₂ production are achieved. In vitro and vivo experiments have demonstrated that BIBCl–PAE NPs are effective in targeting and inhibiting carcinoma. BIBCl–PAE NPs show superior anticancer efficiency relative to non-activatable controls.

The “dual lock-and-key” supramolecular photosensitizers enable specific and enhanced photodynamic therapy (PDT).     

Hydrogen and proton exchange at carbon. Imbalanced transition state and mechanism crossover

A recent remarkable study of the C–H oxidation of substituted fluorenyl-benzoates together with the transfer of a proton to an internal receiving group by means of electron transfer outer-sphere oxidants, in the noteworthy absence of hydrogen-bonding interactions, is taken as an example to uncover the existence of a mechanism crossover, making the reaction pass from a CPET pathway to a PTET pathway as the driving force of the global reaction decreases. This was also the occasion to stress that considerations based on “imbalanced” or “asynchronous” transition states cannot replace activation/driving force models based on the quantum mechanical treatment of both electrons and transferring protons.

Using the remarkable study of C–H oxidation of substituted fluorenyl-benzoates as an example, we have shown that a mechanism crossover takes place upon decreasing the driving force, from a CPET pathway to a PTET pathway.     

Accessing lanthanide-based,in situ illuminated optical turn-on probes by modulation of the antenna triplet state energy

Luminescent lanthanides possess ideal properties for biological imaging, including long luminescent lifetimes and emission within the optical window. Here, we report a novel approach to responsive luminescent Tb(iii) probes that involves direct modulation of the antenna excited triplet state energy. If the triplet energy lies too close to the ⁵D₄ Tb(iii) excited state (20 500 cm⁻¹), energy transfer to ⁵D₄ competes with back energy transfer processes and limits lanthanide-based emission. To validate this approach, a series of pyridyl-functionalized, macrocyclic lanthanide complexes were designed, and the corresponding lowest energy triplet states were calculated using density functional theory (DFT). Subsequently, three novel constructs L3 (nitro-pyridyl), L4 (amino-pyridyl) and L5 (fluoro-pyridyl) were synthesized. Photophysical characterization of the corresponding Gd(iii) complexes revealed antenna triplet energies between 25 800 and 30 400 cm⁻¹ and a 500-fold increase in quantum yield upon conversion of Tb(L3) to Tb(L4) using the biologically relevant analyte H₂S. The corresponding turn-on reaction can be monitored using conventional, small-animal optical imaging equipment in presence of a Cherenkov radiation emitting isotope as an in situ excitation source, demonstrating that antenna triplet state energy modulation represents a viable approach to biocompatible, Tb-based optical turn-on probes.

The rational, analyte-mediated modulation of the relative energy of the lanthanide-sensitizing triplet state produces Tb-based luminescence, observable by a conventional optical imager in presence of the Cherenkov radiation emitting radioisotope ¹⁸F.     

Rational design of an “all-in-one” phototheranostic

We report here porphodilactol derivatives and their corresponding metal complexes. These systems show promise as “all-in-one” phototheranostics and are predicated on a design strategy that involves controlling the relationship between intersystem crossing (ISC) and photothermal conversion efficiency following photoexcitation. The requisite balance was achieved by tuning the aromaticity of these porphyrinoid derivatives and forming complexes with one of two lanthanide cations, namely Gd³⁺ and Lu³⁺. The net result led to a metalloporphodilactol system, Gd-trans-2, with seemingly optimal ISC efficiency, photothermal conversion efficiency and fluorescence properties, as well as good chemical stability. Encapsulation of Gd-trans-2 within mesoporous silica nanoparticles (MSN) allowed its evaluation for tumour diagnosis and therapy. It was found to be effective as an “all-in-one” phototheranostic that allowed for NIR fluorescence/photoacoustic dual-modal imaging while providing an excellent combined PTT/PDT therapeutic efficacy in vitro and in vivo in 4T1-tumour-bearing mice.

We report here porphodilactol derivatives and their corresponding metal complexes as “all-in-one” phototheranostics by controlling the relationship between intersystem crossing (ISC) and photothermal conversion efficiency following photoexcitation.     

A new pentacyclic pyrylium fluorescent probe that responds to pH imbalance during apoptosis

Efficient fluorophores with easy synthetic routes and fast responses are of great importance in clinical diagnostics. Herein, we report a new, rigid pentacyclic pyrylium fluorophore, PS-OMe, synthesised in a single step by a modified Vilsmeier–Haack reaction. Insights into the reaction mechanism facilitated a new reaction protocol for the efficient synthesis of PS-OMe which upon demethylation resulted in a “turn-on” pH sensor, PS-OH. This new fluorescent probe has been successfully used to monitor intracellular acidification at physiological pH. From the fluorescence image analysis, we were able to quantify the intracellular dynamic pH change during apoptosis. This new pH probe is a potential chemical tool for screening, drug discovery and dose determination in cancer therapy.

A modified Vilsmeier–Haack reaction resulted in the synthesis of a pyrylium based turn-on fluorescent pH probe. The probe can monitor minute acidification and dynamic pH variation in cells during apoptosis with therapeutic chemo drugs.     

DNA-templated control of chirality and efficient energy transport in supramolecular DNA architectures with aggregation-induced emission

Two conjugates of tetraphenylethylene with d-2′-deoxyuridine (1d) and l-2′-deoxyuridine (1l) were synthesized to construct new supramolecular DNA-architectures by self-assembly. The non-templated assemblies of 1d and 1l show strong aggregation-induced emission and their chirality is exclusively controlled by the configuration of their sugar part. In contrast, the chirality of the DNA-templated assemblies is governed by the configuration of the DNA, and there is no configuration-selective binding of 1d to d-A₂₀ and 1l to l-A₂₀. The quantum yield of the assembly of 1d along the single-stranded DNA A₂₀ is 0.40; approximately every second available binding site on the DNA template is occupied by 1d. The strong aggregation-induced emission of these DNA architectures can be efficiently quenched and the excitation energy can be transported to Atto dyes at the 5′-terminus. A multistep energy transport “hopping” precedes the final energy transfer to the terminal acceptor. The building block 1d promotes this energy transport as stepping stones. This was elucidated by reference DNA double strands in which 1d was covalently incorporated at two distinct sites in the sequences, one near the Atto dye, and one farther away. This new type of completely self-assembled supramolecular DNA architecture is hierarchically ordered and the DNA template controls not only the binding but also the energy transport properties. The high intensity of the aggregation-induced emission and the excellent energy transport properties make these DNA-based materials promising candidates for optoelectronic applications.

DNA architectures with tetraphenylethylene are assembled in a non-covalent way. The strong aggregation-induced emission of the chromophores is quenched and the energy is transported to Atto dyes by a multistep energy “hopping”.     

Cooperatively assembled liquid crystals enable temperature-controlled Förster resonance energy transfer

Balancing the rigidity of a π-conjugated structure for strong emission and the flexibility of liquid crystals for self-assembly is the key to realizing highly emissive liquid crystals (HELCs). Here we show that (1) integrating organization-induced emission into dual molecular cooperatively-assembled liquid crystals, (2) amplifying mesogens, and (3) elongating the spacer linking the emitter and the mesogen create advanced materials with desired thermal–optical properties. Impressively, assembling the fluorescent acceptor Nile red into its host donor designed according to the aforementioned strategies results in a temperature-controlled Förster resonance energy transfer (FRET) system. Indeed, FRET exhibits strong S-curve dependence as temperature sweeps through the liquid crystal phase transformation. Such thermochromic materials, suitable for dynamic thermo-optical sensing and modulation, are anticipated to unlock new and smart approaches for controlling and directing light in stimuli-responsive devices.

A temperature-sensitive Förster resonance energy transfer system was constructed using a highly emissive liquid crystal co-assembled with Nile red, enabling thermo-optical modulation for controlling and directing light in stimuli-responsive devices.     

Converting molecular luminescence to ultralong room-temperature phosphorescence via the excited state modulation of sulfone-containing heteroaromatics

Manipulating the molecular orbital properties of excited states and the subsequent relaxation processes can greatly alter the emission behaviors of luminophores. Herein we report a vivid example of this, with luminescence conversion from thermally activated delayed fluorescence (TADF) to ultralong room-temperature phosphorescence (URTP) via a facile substituent effect on a rigid benzothiazino phenothiazine tetraoxide (BTPO) core. Pristine BTPO with multiple heteroatoms shows obvious intramolecular charge transfer (ICT) excited states with small exchange energy, featuring TADF. Via delicately functionalizing the BTPO core with peripheral moieties, the excited states of the BTPO derivatives become a hybridized local and charge transfer (HLCT) state in the S₁ state and a local excitation (LE) dominated HLCT state in the T₁ state, with enlarged energy bandgaps. Upon dispersion in a polymer matrix, the BTPO derivatives exhibit a persistent bright green afterglow with long lifetimes of up to 822 ms and decent quantum yields of up to 11.6%.

The decoration of a BTPO core results in a change in the luminescence nature from TADF to URTP. The phosphors in an amorphous PMMA matrix showed monomeric URTP with phosphorescence lifetimes of up to 822 ms and quantum yields of up to 11.6%.     

Quantifying internal charge transfer and mixed ion-electron transfer in conjugated radical polymers

Macromolecular radicals are receiving growing interest as functional materials in energy storage devices and in electronics. With the need for enhanced conductivity, researchers have turned to macromolecular radicals bearing conjugated backbones, but results thus far have yielded conjugated radical polymers that are inferior in comparison to their non-conjugated partners. The emerging explanation is that the radical unit and the conjugated backbone (both being redox active) transfer electrons between each other, essentially “quenching” conductivity or capacity. Here, the internal charge transfer process is quantified using a polythiophene loaded with 0, 25, or 100% nitroxide radicals (2,2,6,6-tetramethyl-1-piperidinyloxy [TEMPO]). Importantly, deconvolution of the cyclic voltammograms shows mixed faradaic and non-faradaic contributions that contribute to the internal charge transfer process. Further, mixed ion-electron transfer is determined for the 100% TEMPO-loaded conjugated radical polymer, from which it is estimated that one triflate anion and one propylene carbone molecule are exchanged for every electron. Although these findings indicate the reason behind their poor conductivity and capacity, they point to how these materials might be used as voltage regulators in the future.

Conjugated radical polymers can exhibit internal electron transfer depending on the radical loading.     

Thermo- and light-triggered reversible interconversion of dysprosium–anthracene complexes and their responsive optical,magnetic and dielectric properties

Artificial smart materials with switchable multifunctionality are of immense interest owing to their wide application in sensors, displays and memory devices. Lanthanide complexes are promising multifunctional materials integrating optical and magnetic characteristics. However, synergistic manipulation of different physical properties in lanthanide systems is still challenging. Herein we designed and synthesized a mononuclear complex [Dy^III(SCN)₃(depma)₂(4-hpy)₂] (1), which incorporates 9-diethylphosphonomethylanthracene (depma) as a photo-active component and 4-hydroxypyridine (4-hpy) as a polar component. This compound shows several unusual features: (a) reversible thermo-responsive phase transition associated with the order–disorder transition of 4-hpy and SCN⁻, which leads to thermochromic behavior and dielectric anomaly; (b) reversible photo-induced dimerization of anthracene groups, which leads to synergistic switching of luminescence, magnetic and dielectric properties. To our knowledge, compound 1 is the first example of lanthanide complexes that show stimuli-triggered synergistic and reversible switching of luminescence, magnetic and dielectric properties.

[Dy^III(SCN)₃(depma)₂(4-hpy)₂] (1) shows reversible thermo-induced phase transition associated with thermochromism and dielectric anomaly and photo-induced dimerization with synergistic switching of luminescence, magnetic and dielectric properties.     

Insight into the drastically different triplet lifetimes of BODIPY obtained by optical/magnetic spectroscopy and theoretical computations

The triplet state lifetimes of organic chromophores are crucial for fundamental photochemistry studies as well as applications as photosensitizers in photocatalysis, photovoltaics, photodynamic therapy and photon upconversion. It is noteworthy that the triplet state lifetime of a chromophore can vary significantly for its analogues, while the exact reason was rarely studied. Herein with a few exemplars of typical BODIPY derivatives, which show triplet lifetimes varying up to 110-fold (1.4–160 μs), we found that for these derivatives with short triplet state lifetimes (ca. 1–3 μs), the electron spin polarization (ESP) pattern of the time-resolved electron paramagnetic resonance (TREPR) spectra of the triplet state is inverted at a longer delay time after laser pulse excitation, as a consequence of a strong anisotropy in the decay rates of the zero-field state sublevel of the triplet state. For the derivatives showing longer triplet state lifetimes (>50 μs), no such ESP inversion was observed. The observed fast decay of one sublevel is responsible for the short triplet state lifetime; theoretical computations indicate that it is due to a strong coupling between the T_z sublevel and the ground state mediated by the spin–orbit interaction. Another finding is that the heavy atom effect on the shortening of the triplet state lifetime is more significant for the T₁ states with lower energy. To the best of our knowledge, this is the first systematic study to rationalize the short triplet state lifetime of visible-light-harvesting organic chromophores. Our results are useful for fundamental photochemistry and the design of photosensitizers showing long-lived triplet states.

The electron spin polarization inversion and anisotropic decay of triplet substates explain the short triplet state lifetime of BODIPY derivatives.     

Photo-modulated wide-spectrum chromism in Eu3+ and Eu3+/Tb3+ photochromic coordination polymer gels: application in decoding secret information

Photo-switching emission of photochromic materials has paramount importance in the field of optoelectronics. Here, we report synthesis and characterization of a dithienylethene (DTE) based photochromic low molecular weight gelator (LMWG) and self-assembly with lanthanide (Eu³⁺ and Tb³⁺) ions to form a photochromic coordination polymer gel (pcCPG). Based on DTE ring opening and closing, the TPY-DTE gel shuttles from pale-yellow coloured TPY-DTE-O to dark blue coloured TPY-DTE-C and vice versa upon irradiating with UV and visible light, respectively, and both the photoisomers show distinct optical properties. Furthermore, integration of Eu³⁺ and Tb³⁺ lanthanides with TPY-DTE resulted in red and green emissive Eu-pcCPG (Q.Y. = 18.7% for the open state) and Tb-pcCPG (Q.Y. = 23.4% for the open state), respectively. The photoisomers of Eu-pcCPG exhibit photo-switchable spherical to fibrous reversible morphology transformation. Importantly, an excellent spectral overlap of the Eu³⁺ centred emission and absorption of DTE in the closed form offered photo-switchable emission properties in Eu-pcCPG based on pcFRET (energy transfer efficiency >94%). Further, owing to the high processability and photo-switchable emission, the Eu-pcCPG has been utilized as invisible security ink for protecting confidential information. Interestingly, mixed Eu³⁺/Tb³⁺ pcCPG exhibited photo-modulated multi-spectrum chromism reversibly where the colour changes from yellow, blue, and red to green and vice versa under suitable light irradiation.

A lanthanide based photochromic coordination polymer gel (pcCPG) material has been developed which showed photomodulated colour change based on pcFRET and has the potential to be employed for decoding secret information.