and the localization of the TH
+
, despite of this difficulty. They found that TH
+ is
aligned parallel to the 12MR and located on the mirror planes parallel to the c-axis.
Water molecules interact strongly with the dye and form a kind of solvent-matrix
tube shaped around the TH
+ [19].
Perylene dyes have been used in many dye-ZL composites because of their
spectroscopic properties and their chemical robustness which allow preparing systems with a large variety of interesting properties [14, 16, 46, 83, 87, 159, 162–
164]. Knowing details regarding the structural characteristics of such composites is
therefore important. Hence, it is satisfactory that Gigli et al. have been able to
establish a microscopically detailed picture of a hybrid composite of ZL with the
perylene diimide tb-DXP at both hydrated and anhydrous conditions by applying
integrating experiments with different time scale and radiation source (IR, XRPD,
total scattering), including first-principles DFT modeling [44]. A graphical representation of the results is seen in Fig. 15. The asymmetric positioning of the dye in
Fig. 15 Structure of a hybrid tb-DXP-ZL composite. (a) Graphical representation of the minimum
energy structure of the anhydrous tb-DXP-ZL system. Only the Al/Si atoms of the framework (gray
sticks) are represented. C atoms are represented in cyan, N in blue, O in red, and H in white. The K
+
are shown as purple spheres. (b) Optimized structure of the hydrated tb-DXP-ZL. (c) The tb-DXP
molecule extracted from the optimized anhydrous system, along with the four closest potassium
cations. (d) The tb-DXP molecule extracted from the optimized hydrated system. Also shown are
the four closest K
+ and the water molecules hydrogen bonded (red-dashed lines) to the carbonyl
oxygen atoms. The framework oxygen atoms (yellow spheres) close to the potassium cations are
shown as well in (c) and (d). In panels c and d, the four shortest K
+ ÁÁÁOCO distances (in Å) are
indicated [44]. Adapted with permission from [44] Copyright American Chemical Society
30
G. Calzaferri
+
, despite of this difficulty. They found that TH
+ is
aligned parallel to the 12MR and located on the mirror planes parallel to the c-axis.
Water molecules interact strongly with the dye and form a kind of solvent-matrix
tube shaped around the TH
+ [19].
Perylene dyes have been used in many dye-ZL composites because of their
spectroscopic properties and their chemical robustness which allow preparing systems with a large variety of interesting properties [14, 16, 46, 83, 87, 159, 162–
164]. Knowing details regarding the structural characteristics of such composites is
therefore important. Hence, it is satisfactory that Gigli et al. have been able to
establish a microscopically detailed picture of a hybrid composite of ZL with the
perylene diimide tb-DXP at both hydrated and anhydrous conditions by applying
integrating experiments with different time scale and radiation source (IR, XRPD,
total scattering), including first-principles DFT modeling [44]. A graphical representation of the results is seen in Fig. 15. The asymmetric positioning of the dye in
Fig. 15 Structure of a hybrid tb-DXP-ZL composite. (a) Graphical representation of the minimum
energy structure of the anhydrous tb-DXP-ZL system. Only the Al/Si atoms of the framework (gray
sticks) are represented. C atoms are represented in cyan, N in blue, O in red, and H in white. The K
+
are shown as purple spheres. (b) Optimized structure of the hydrated tb-DXP-ZL. (c) The tb-DXP
molecule extracted from the optimized anhydrous system, along with the four closest potassium
cations. (d) The tb-DXP molecule extracted from the optimized hydrated system. Also shown are
the four closest K
+ and the water molecules hydrogen bonded (red-dashed lines) to the carbonyl
oxygen atoms. The framework oxygen atoms (yellow spheres) close to the potassium cations are
shown as well in (c) and (d). In panels c and d, the four shortest K
+ ÁÁÁOCO distances (in Å) are
indicated [44]. Adapted with permission from [44] Copyright American Chemical Society
30
G. Calzaferri