Mimicking such functional control in synthetic nanopores requires precise control of structure and local placement of surface functionality. Such precisely prepared materials with nanoscale control on structure and functionalization would allow, for example, new perspectives in sensing. [1] Further strategies mimicking the functionality of biological channels include dynamic curvature nanochannel-based membranes to regulate ionic transport [2] or flexible elastomer-based microchannels for microfluidic devices. [3] Already today nanoscopically structured materials play a crucial role in applications such as sensors or lab on chip devices, [4] separation, [4d] catalysis, [5] and for the developing of new materials, for example for applications in tissue engineering [6] or for the control of surface wettability. [7] Traditionally, nanostructures are fabricated using top-down approaches like photolithography, ink-jet printing or electrospinning. Alternatively, bottom-up methods, which are based on the self-assembly of molecules or larger building blocks, can yield defined structures with high resolution. [8] Periodic, nanostructured materials are for example accessible through the self-assembly of colloidal building blocks, which can yield macroscopic areas of wellordered colloidal crystals. [9] Such colloidal crystals can be further used as templates to generate inorganic, interconnected nanopore arrays by backfilling with a sol-gel precursor and subsequent removal of the templating particles. [9a,10] In two dimensions, the resulting porous materials are known as inverse colloidal monolayers and their wettability can be adjusted by pore opening angle and surface functionalization. [7e,11] Such structures are ideal model pores due to their uniformity, adjustable pore size and ordered structure.A key step toward multifunctional nanopores with nanolocal control, is the ability to precisely position different functionalities into individual pores. [1a] Therefore, it is necessary to develop strategies for a nanoscale control in manufacturing and functionalization of porous materials. This enables nanopore design with multiple functional and responsive units, individually and precisely placed into each nanopore. [1b] To date, functionalization of porous silica materials is mainly based on postsynthetic functionalization strategies like grafting of silanes from gas or liquid phase or cocondensation of functional building blocks. [12] These approaches generally result in a homogenous functionalization without In the context of sensing and transport control, nanopores play an essential role. Designing multifunctional nanopores and placing multiple surface functionalities with nanoscale precision remains challenging. Interface effects together with a combination of different materials are used to obtain local multifunctionalization of nanoscale pores within a model pore system prepared by colloidal templating. Silica inverse colloidal monolayers are first functionalized with a gold layer to create a hybrid porous ...

Plasmonic complementary structures are interesting model systems that combine propagating and localized surface plasmon resonances and allow the fundamental study of their hybridization. In the simplest form, such structures are formed by stacking arrays of nanodisks and nanoholes with matching dimensions. Here, we produce such hole-disk arrays in an experimentally easy and parallel colloidal lithography process with accurate control over vertical alignment and separation between the individual disks and holes. Importantly, our process readily enables symmetry breaking and the design of asymmetric hole-disk arrays with controlled lateral offset between each holedisk pair. We investigate the coupling between the parental resonances of the two elements as a function of feature size and separation distance and provide a plasmon hybridization scheme to rationalize the resonances. We find that for the asymmetric hole-disk structure, a new, hybrid resonance arises as a peak in the transmission spectra, which is not found in their symmetric analogues. We demonstrate that this new resonance imparts a higher sensitivity in refractive index sensing as it features a pronounced near-field enhancement in between holes and disks. The near-field structure, paired with the accessibility of this separation region in the presented hole-disk structures, implies that this architecture should be sensitive to local changes in the refractive index at the surface of the dielectric layer separating the plasmonic elements. We demonstrate this sensitivity of the asymmetric hole-disk arrays by the detection of the binding of a silane monolayer at the walls of the dielectric silica spacer layer.

Functionalized nanopores have attracted strong interest in different fields in which nanopore transport is essential. Detailed insights into mass transport through nanopores and its correlation to pore wall properties such as wettability are essential. The potential and challenges using electrochemical impedance spectroscopy (EIS) to analyze mass transport through mesoporous silica thin films with precisely adjusted wettability are discussed. The accessible area of the electrode, the charge transfer or film resistance and the diffusion coefficients of the redox probe [Ru(NH3)6]2+/3+ inside the mesopores are determined. The influence of experimental parameters such as silica film pre‐treatment is evaluated. Hydrophilic mesoporous films display comparable diffusion coefficients around 1*10–8 cm2 s–1 independently of the exact wettability. As expected, hydrophobic films do not exhibit transport due to water exclusion. The sample pre‐treatment strongly influences the transport characteristics. Incubation into aqueous KCl leads to a decrease in the resistance for all tested mesoporous films. This is ascribed to an increase in the silanol group concentration at the pore wall. Besides the insights into mass transport in mesoporous films and on how to measure EIS in such films, this study elucidates the importance of sample pre‐treatment and surface chemistry concerning mesoporous film performance.

Exciplex or excited complex emission is an excited state process, arising from considerable charge transfer of an excited energy donor to an acceptor, which can be identified by the occurrence of a redshifted emission band that is absent in the individual constituents. Particularly interesting are exciplexes that are formed by intramolecular excited state interaction, which are inherently concentration independent. Based upon our previous experience in the Ugi-4CR syntheses of donor-acceptor conjugates capable of photo-induced intramolecular electron transfer (PIET), that is, generation of light-induced charge separation, we now disclose the diversity-oriented approach on unimolecular exciplex emitters and their reference systems by Ugi-4CR. The photophysics is studied by absorption and emission spectroscopy and accompanied by density functional theory (DFT) and time-dependent density functional theory (TDDFT) calculations.