Kurita, N.

Natsume, T.

Sengoku, Y.

Starikov, E. B.

Tanaka, S.

Wenzel, W.

English

KITopen

allows for much milder reaction conditions because HKUST 1MOFs can be fabricated at room temperature; in conventionalsolvothermal synthesis, typically temperatures above 100 °C areemployed. The LPE process used here was modified relative toone described in earlier work33 by introducing an additional step,immersion into a solution of Ti MOC, after the H3BTC step.We used the spray version of the LPE process34 and appliedCu(OAc)2, H3BTC, and Ti MOC in a sequential fashion(Figure S2). Between each step, the substrate was rinsed withpure ethanol.The LPE process was developed originally for the preparationof thin, high quality MOF coatings to be used as model systemsfor studying, for example, fundamental processes (diffusion,optical, and electrical properties13,35−37) of MOFs. An importantadvantage of the LPE process is that the resulting materialis obtained in the form of monolithic thin films, which allow,for example, the fabrication of sensors,13,38 high qualitymembranes,39 and electrodes to be used in electrochemistry ina straightforward fashion.After 60 LPE cycles, a thin MOF film was obtained, which inthe following is referred to as (HKUST 1)(Ti MOC) SURMOF.XRD scans recorded in an out of plane geometry for a HKUST 1SURMOF grown on a COOH terminated substrate (Figure 1c)revealed peaks at 6.8° and 13.6°, identified as the (200) and(400) reflections of HKUST 1, demonstrating the presenceof a well defined, highly oriented HKUST 1 thin film, in analogyto previous work.33 The absence of diffraction peaks for otherHKUST 1 orientations demonstrated the presence of anoriented thin film, with the [100] orientation perpendicular tothe substrate (Figure 1c). XRD data recorded for the NP loaded(HKUST 1)(Ti MOC) SURMOF (see Figure 1c) revealed adegree of crystallinity similar to that of the empty MOF.The infrared reflection absorption spectroscopy of Ti MOC@HKUST 1 showed that the absorbance bands at 1323, 1240, and982 cm−1 are ascribed to C−O vibrations of Ti MOC (Figure 1d).Note that the relative intensities of the (400) and (200) diffractionpeaks were strongly different after loading with the Ti MOC,revealing that within the host framework, a periodic array ofTi MOC NPs had formed. Based on these results, we propose astructural model in which each large pore of the HKUST 1SURMOF contains one MOC particle (Figure 1b). Comparisonof XRD simulations carried out for this model with theexperimental data (see Figure 1c) reveals good agreement.SEM images (Figure 2), TEM images, and electron mapping(Figure 3) recorded for the (HKUST 1)(Ti MOC) thin filmsshow that the Ti MOC guests loaded in HKUST 1 have acompact and homogeneous distribution. Presumably because ofa low threshold for beam damage, individual NPs could not beresolved. The TEM EDS data (Figure 3a) and the SEM EDSdata of a sample cross section both gave a Cu/Ti molar ratioof 3:1. The ratio between Cu atoms and the large pores inHKUST 1 was to 12:1.40 Considering that each Ti MOCcontains four Ti atoms, we conclude that virtually every largepore in our HKUST 1MOF thin films contains a chiral Ti MOC,in accord with the model proposed above. The IR absorbancebands at 1323, 1240, and 982 cm−1 are ascribed to C−Ovibrations of R Ti MOC and demonstrate that the Ti MOCloaded into the MOF cages is fully intact.To demonstrate the huge potential of these porous homochiral metacrystals, (HKUST 1)(Ti MOC), SURMOFs wereFigure 1. (a) Structure of the R Ti MOC clusters. (b) Schematic presentation of in situ layer by layer growth of enantiopure Ti MOC loadedHKUST 1 thin film using liquid phase epitaxy (LPE) approach. Characterization of chiral Ti MOC loaded HKUST 1 thin film via an in situ lblLPE approach: (c) XRD and (d) IRRAS (infrared reflection absorption spectroscopy).grown on OH functionalized quartz glass substrates, which allowrecording of CD data.41 The CD spectrum recorded for such thinfilms (which on this surface grow along the different, (111)orientation; Figure S3) is almost identical to that of R Ti MOC(Figure 4a) but different from spectra recorded for the freeR BINOL ligands recorded in solution. This observation confirmsagain the successful encapsulation of intact Ti MOCs into theHKUST 1 thin film. In the following, R Ti MOC (S Ti MOC)denotes a Ti MOC with R binol (S binol) ligands. Correspondingly, (HKUST 1)(X Ti MOC) is a HKUST 1 loaded withX Ti MOC, with X = R or X = S.Moreover, the ESI (electron spray ionization) mass spectrumstudy (Figure 5a) combined with identical liquid and solid CDspectra (Figure 5b) of the chosen Ti MOCs demonstrates thatthe Ti MOC is stable in ethanol/DMF solution; leaching ofTi MOCs out of the NP@MOF structure was not observed.Identical results were obtained when loading with S Ti MOC(Figure 4a).The UV−vis spectrum (Figure 6) shows the presence of asmooth homogeneous film of optical quality comparable to thatof the pristine HKUST 1 SURMOF.To illustrate the general nature of our new lbl embeddingapproach, we also have demonstrated the encapsulation methodfor other MOF hosts, including Cu(bdc) SURMOF 242and a Cu2(D cam)2dabco layer pillar type MOF43 (bdc =1,4benzenedicarboxylate; D cam = (1R,3S) camphorate andFigure 3. 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Investigation of a Kubo-formula-based approach to estimate DNA conductance in an atomistic model

https://publikationen.bibliothek.kit.edu/1000012192/150079176

Investigation of a Kubo-formula-based approach to estimate DNA conductance in an atomistic model

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