ABSTRACT
The introduction of metal sites into molecular metal oxides, so-called polyoxometalates, is key for tuning their structure and reactivity. The complex mechanisms which govern metal-functionalization of polyoxometalates are still poorly understood. Here, we report a coupled set of light-dependent and light-independent reaction equilibria controlling the mono- and di-metal-functionalization of a prototype molecular vanadium oxide cluster. Comprehensive mechanistic analyses show that coordination of a Mg2+ ion to the species {(NMe2H2)2[VV12O32Cl]}3- results in formation of the mono-functionalized {(NMe2H2)[(MgCl)VV12O32Cl]}3- with simultaneous release of a NMe2H2+ placeholder cation. Irradiation of this species with visible light results in one-electron reduction of the vanadate, exchange of the second NMe2H2+ with Mg2+, and formation/crystallization of the di-metal-functionalized [(MgCl)2VIVVV11O32Cl]4-. Mechanistic studies show how stimuli such as light or competing cations affect the coupled equilibria. Transfer of this synthetic concept to other metal cations is also demonstrated, highlighting the versatility of the approach.
ABSTRACT
The self-assembly of molecular metal oxides, polyoxometalates (POMs), can be controlled using internal or, more rarely, external templates. Here, we explore how the interplay between internal templates (halides, oxoanions) and organic external templates (protonated cyclene species) affect the self-assembly of a model polyoxovanadate cluster, [V12O32X]n- (X = Cl-, Br-, NO3-). A combination of crystallographic analyses, spectroscopic studies and in situ as well as solid-state 51V NMR spectroscopy provide critical insights into the initial formation of an intermediate vanadate species formed during the process. Structural and spectroscopic studies suggest that a direct interaction between internal and external templates allows tuning of the internal template position within the cluster cavity. These insights form the basis for further developing the template-driven synthetic chemistry of polyoxovanadates.
ABSTRACT
Metal cations are used to control the selective crystallization of organic-inorganic supramolecular polymers. Two complementary monomers, a dodecanuclear vanadate [V12O32(NO3)]5- and the organic macrocycle cyclen assemble into hybrid host-guest aggregates. In the presence of Ba2+ or La3+, supramolecular polymerization and crystallization is driven by a complex interplay of cyclene protonation, hydrogen-bonding and electrostatics.
ABSTRACT
Bare gold nanoparticles were embedded into an iron-polyoxovanadate matrix and used to enhance both the infrared and Raman signatures of a model analyte. A detailed characterization of the matrix-embedded nanoparticles revealed that they retained a plasmon resonance at 564 nm. The enhancement of vibrational signatures of the model analyte crystal violet using bare and embedded gold nanoparticles was compared for both surface enhanced infrared (SEIRA) spectroscopy and surface enhanced Raman spectroscopy (SERS) yielding enhancement factors of 2.2 for SEIRA and 77 for SERS. In contrast, the bare gold nanoparticles revealed significantly lower enhancements (1.6 for SEIRA; 20 for SERS). Hence, it was shown that embedding nanoparticles within an inorganic polyoxometalate-based matrix is an innovative strategy to amplify their signal enhancement properties in vibrational spectroscopies.
ABSTRACT
The reliable online analysis of volatile compounds in exhaled breath remains a challenge, as a plethora of molecules occur in different concentration ranges (i.e., ppt to %) and need to be detected against an extremely complex background matrix. Although this complexity is commonly addressed by hyphenating a specific analytical technique with appropriate preconcentration and/or preseparation strategies prior to detection, we herein propose the combination of three different detector types based on truly orthogonal measurement principles as an alternative solution: Field-asymmetric ion mobility spectrometry (FAIMS), Fourier-transform infrared (FTIR) spectroscopy-based sensors utilizing substrate-integrated hollow waveguides (iHWG), and luminescence sensing (LS). By carefully aligning the experimental needs and measurement protocols of all three methods, they were successfully integrated into a single compact analytical platform suitable for online measurements. The analytical performance of this prototype system was tested via artificial breath samples containing nitrogen (N2), oxygen (O2), carbon dioxide (CO2), and acetone as a model volatile organic compound (VOC) commonly present in breath. All three target analytes could be detected within their respectively breath-relevant concentration range, i.e., CO2 and O2 at 3-5 % and at ~19.6 %, respectively, while acetone could be detected with LOQs as low as 165-405 ppt. Orthogonality of the three methods operating in concert was clearly proven, which is essential to cover a possibly wide range of detectable analytes. Finally, the remaining challenges toward the implementation of the developed hybrid FAIMS-FTIR-LS system for exhaled breath analysis for metabolic studies in small animal intensive care units are discussed.
