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Two nanosensors for simultaneous optical measurements of the bioanalytically and biologically relevant analytes temperature (“T”), oxygen (“O”), and pH (“P”) have been designed. These “TOP” nanosensors are based on 100 nmsized silica-coated polystyrene nanoparticles (PS-NPs) doped with a near-infrared emissive oxygen- and temperature-sensitive chromium(III) complex ([Cr(ddpd)2][BPh4]3, CrBPh4) and an inert reference dye (Nile Red, NR or 5,10,15,20tetrakis(pentafluorophenyl) porphyrin, TFPP) and are covalently labeled with pHsensitive fluorescein isothiocyanate (FITC). These emitters can be excited at the same wavelength and reveal spectrally distinguishable emission bands, allowing for ratiometric intensity-based and time-resolved studies in the visible and near-infrared wavelength region. Studies in PBS buffer solutions and in a model body liquid demonstrate the applicability of these nanosensors for the sensitive luminescence readout of TOP simultaneously at the same spatialposition.
Two nanosensors for simultaneous optical measurements of temperature (“T”), oxygen (“O”), and pH (“P”) have been designed. These “TOP” nanosensors are based on 100 nm-sized silica-coated polystyrene nanoparticles (PS-NPs) doped with the near infrared emissive oxygen- and temperature-sensitive chromium(III) complex ([Cr(ddpd)2][BPh4]3 CrBPh4)[1][2] and an inert reference fluorescence dye (Nile Red NR or 5,10,15,20tetrakis-(pentafluorophenyl) porphyrin TFPP) and are covalently labeled with the pHsensitive fluorophore fluorescein isothiocyanate (FITC). These emitters can be excited at the same wavelength and reveal distinguishable emission spectra suitable for ratiometric intensity-based and time-resolved studies in the visible and near infrared spectral region. The core-shell nanostructure of these sensors reveals high colloidal stability in various aqueous media. Studies in PBS buffer solutions and in a model body liquid demonstrate the applicability of the TOP nanosensors for optically detecting the three bioanalytically and biologically relevant analytes temperature, oxygen and pH simultaneously at the same position.
Two nanosensors for simultaneous optical measurements of temperature (“T”), oxygen (“O”), and pH (“P”) have been designed. These “TOP” nanosensors are based on 100 nm-sized silica-coated polystyrene nanoparticles (PS-NPs) doped with the near infrared emissive oxygen- and temperature-sensitive chromium(III) complex ([Cr(ddpd)2][BPh4]3 CrBPh4)[1][2] and an inert reference fluorescence dye (Nile Red NR or 5,10,15,20-tetrakis-(pentafluorophenyl) porphyrin TFPP) and are covalently labeled with the pH-sensitive fluorophore fluorescein isothiocyanate (FITC). These emitters can be excited at the same wavelength and reveal distinguishable emission spectra suitable for ratiometric intensity-based and time-resolved studies in the visible and near infrared spectral region. The core-shell nanostructure of these sensors reveals high colloidal stability in various aqueous media. Studies in PBS buffer solutions and in a model body liquid demonstrate the applicability of the TOP nanosensors for optically detecting the three bioanalytically and biologically relevant analytes temperature, oxygen and pH simultaneously at the same position.
Sensitized triplet-triplet annihilation upconversion (sTTA-UC) mainly relies on precious metal complexes thanks to their high intersystem crossing (ISC) efficiencies, excited state energies, and lifetimes, while complexes of abundant first-row transition metals were only rarely utilized and with often moderate UC quantum yields. [Cr(bpmp)2]3+ (bpmp = 2,6-bis(2-pyridylmethyl)pyridine) containing earth-abundant chromium possesses an absorption band suitable for green light excitation, a doublet excited state energy matching the triplet energy of 9,10-diphenyl anthracene (DPA), a close to millisecond excited state lifetime, and high photostability. Combined ISC and doublet-triplet energy transfer from excited [Cr(bpmp)2]3+ to DPA gives 3DPA with close-to-unity quantum yield. TTA of 3DPA furnishes greento-blue UC with a quantum yield of 12.0 % (close to the theoretical maximum). Sterically less-hindered anthracenes undergo a [4+4] cycloaddition with [Cr(bpmp)2]3+ and green light.
The molecular ruby analogue [Cr(ddpd)2]3+ (ddpd=N,N’-dimethyl-N,N’-dipyridine-2-ylpyridine-2,6-diamine) exhibits near infrared (NIR) emission with a high photoluminescence (PL) quantum yield ΦPL of 11 % and a lifetime of 898 μs in deaerated water at room temperature. While ligand-based control of the photophysical properties has received much attention, influences of the counter anions and microenvironment are still underexplored. In this study, the luminescence properties of the molecular ruby were systematically examined for the counter anions Cl−, Br−, [BF4]−, [PF6]−, [BPh4]−, and [BArF24]− in acetonitrile (MeCN) solution, in crystals, and embedded into polystyrene nanoparticles (PSNP). Stern-Volmer analyses of the oxygen quenching studies in the intensity and lifetime domain showed the highest oxygen sensitivity of the complexes with the counter anions of [BF4]− and [BArF24]−, which also revealed the longest luminescence lifetimes. Embedding [Cr(ddpd)2][PF6]3 in PSNPs and shielding with poly(vinyl alcohol) yields a strongly NIR-emissive oxygen-insensitive material with a record ΦPL of 15.2 % under ambient conditions.
In summary, we report a highly modular solid TTA-UC system comprising of a crystalline, thermally stable PCN222(Pd) MOF with CA-coated MOF channels and with a DPA annihilator embedded in a solution-like environment in the MOF channels. This solid material displays blue upconverted delayed emission with a luminescence lifetime of 373 us, a threshold value of 329 mW*cm-2 and a triplet–triplet energy transfer efficiency of 82%. This optical application adds another facet to the versatile chemistry of PCN-222 MOFs. The design concept is also applicable to other TTA-UC pairs and enables tuning of the UCL color, for example, by replacing DPA with other dyes as exemplarily shown for 2,5,8,11-tetra-tert-butyl-perylene, that yields UCL at 450 nm. Current work aims to reduce the oxygen sensitivity and to increase the retention of the trapped annihilators in organic environments, for example, by tuning the chain length of the carboxylic acid and by coating the MOF surface. In addition, the TTA-UC efficiency will be further enhanced by reducing the reabsorption of the UC emission caused by Pd(TCPP) and by optimizing the sensitizer/annihilator interface.
In this work, we describe the synthesis, structural and photophysical characterization of four novel Pd(II) and Pt(II) complexes bearing tetradentate luminophoric ligands with high photoluminescence quantum yields (FL) and long excited state lifetimes (s) at room temperature, where the results were interpreted by means of DFT calculations. Incorporation of fluorine atoms into the tetradentate ligand favors aggregation and thereby, a shortened average distance between the metal centers, which provides accessibility to metal–metal-to-ligand charge-transfer (3MMLCT) excimers acting as red-shifted Energy traps if compared with the monomeric entities. This supramolecular approach provides an elegant way to enable room-temperature phosphorescence from Pd(II) complexes, which are otherwise quenched by a thermal population of dissociative states due to a lower ligand field splitting. Encapsulation of These complexes in 100 nm-sized aminated polystyrene nanoparticles enables concentration-controlled aggregation-enhanced dual emission. This phenomenon facilitates the tunability of the absorption and emission colors while providing a rigidified environment supporting an enhanced FL up to about 80% and extended s exceeding 100 ms. Additionally, these nanoarrays constitute rare examples for selfreferenced oxygen reporters, since the phosphorescence of the aggregates is insensitive to external influences, whereas the monomeric species drop in luminescence lifetime and intensity with increasing triplet molecular dioxygen concentrations (diffusion-controlled quenching).
Gaining chemical control over the thermodynamics and kinetics of photoexcited states is paramount to an efficient and sustainable utilization of photoactive transition metal complexes in a plethora of technologies. In contrast to energies of charge Transfer states described by spatially separated orbitals, the energies of spinflip states cannot straightforwardly be predicted as Pauli Repulsion and the nephelauxetic effect play key roles. Guided by multireference quantum chemical calculations, we report a novel highly luminescent spin-flip emitter with a quantum chemically predicted blue-shifted luminescence. The spin-flip emission band of the chromium complex [Cr(bpmp)2]3+ (bpmp = 2,6-bis(2-pyridylmethyl) pyridine) shifted to higher energy from ca. 780 nm observed for known highly emissive chromium(III) complexes to 709 nm. The photoluminescence quantum yields climb to 20%, and very long excited state lifetimes in the millisecond range are achieved at room temperature in acidic D2O solution. Partial ligand deuteration increases the quantum yield to 25%. The high excited state energy of [Cr(bpmp)2]3+ and its facile reduction to [Cr(bpmp)2]2+ result in a high excited state redox potential. The ligand’s methylene bridge acts as a Brønsted acid quenching the luminescence at high pH. Combined with a pH-insensitive chromium(III) emitter, ratiometric optical pH sensing is achieved with single wavelength excitation. The photophysical and Ground state properties (quantum yield, lifetime, redox potential, and acid/base) of this spin-flip complex incorporating an earth-abundant metal surpass those of the classical precious metal [Ru(α-diimine)3]2+ charge transfer complexes, which are commonly employed in optical sensing and photo(redox) catalysis, underlining the bright future of these molecular ruby analogues.
Structural modularity of polymer frameworks is a key advantage of covalent organic polymers, however, only C, N, O, Si and S have found their way into their building blocks so far. Here, we expand the toolbox available to polymer and materials chemists by one additional nonmetal, phosphorus. Starting with a building block that contains a λ⁵‐phosphinine (C₅P) moiety, we evaluate a number of polymerisation protocols, finally obtaining a π‐conjugated, covalent phosphinine‐based framework (CPF‐1) via Suzuki‐Miyaura coupling. CPF‐1 is a weakly porous polymer glass (72.4 m2 g‐1 N2 BET at 77 K) with green fluorescence (λmax 546 nm) and extremely high thermal stability. The polymer catalyzes hydrogen evolution from water under UV and visible light irradiation without the need for additional co‐catalyst at a rate of 33.3 μmol h‐¹ g‐¹. Our results demonstrate for the first time the incorporation of the phosphinine motif into a complex polymer framework. Phosphinine‐based frameworks show promising electronic and optical properties that might spark future interest in their applications in light‐emitting devices and heterogeneous catalysis.
In summary, by combining the NIR-emissive [Cr(ddpd)2][BPh4]3 complex CrBPh4 with its extremely large energy gap between the longest wavelength absorption and emission maxima with a pH-responsive fluorescein derivative (FITC) and an inert reference dye like Nile Red (NR) and 5,10,15,20tetrakis(pentafluorophenyl) porphyrin (TFPP), we developed nanosensors for simultaneously sensing temperature, O2 partial pressure, and pH. These novel TOP nanosensors (temperature, oxygen, pH) cover the biologically and physiologically relevant concentration ranges of these parameters/analytes with single wavelength excitation in PBS buffer and in a cell culture medium containing bovine serum albumin (BSA). The response of both nanosensors to all parameters is fully reversible and only minimally affected by the presence of BSA, the most common serum albumin. Moreover, comparative studies with nanosensors containing only a single type of stimuli-responsive molecule and with the respective molecular systems revealed that the different sensor components do not interfere with each other. Future research will include the testing of these nanosensors in cellular uptake studies and, after surface modification with targeted bioligands, eventually in in vivo experiments as previously done by some of us with other polystyrene nanoparticle reporters and nanosensors.46,47 Moreover, this concept of multianalyte sensing will be expanded to nanosensors derived from differently sized premanufactured biocompatible polymer particles and different stimuli-responsive dyes like fluorescent indicators for biologically and bioanalytically relevant metal ions.