Kristallisation supramolekularer Materialien: Perhydrotriphenylen(PHTP)‐Einschlußverbindungen mit nichtlinearen optischen Eigenschaften

A New Organic Nanoporous Architecture: Dumb-Bell-Shaped Molecules with Guests in Parallel Channels

“…Following the analysis of the pyroelectric effect, we can conclude that BAOT/BU crystals consist (ideally) of two adjacent macro-domains (in real cases often overlapping [28] ) showing an opposite net polarisation. As reported in detail for inclusion compounds of perhydrotriphenylene, [9] application of a homogeneous Markov process is sufficient to explain polarity formation during crystal growth, that is the attachments of dipoles to sites where guest molecules have already entered the channel structure. In the case of BU, a nonvanishing energy difference between (R 2 C O ´´´O CR 2 ) and (RÀCH 3 ´´´H 3 CÀR) is sufficient to give rise to a certain evolution of polarity as crystals grow along their channel axis.…”

“…In our case, the BAOT molecules pack in a centric manner. When a second functional component (9,10,11) is present, we can apply arguments put forward for BU: In the case of 10, functional group interactions of terminal groups such as a dicyano group may be stronger when interacting with BU, than interactions of BU with itself. Although we can understand polar ordering of 9 and 10, it remains open as to why polar ordering of BU is found for BAOT/BU-11.…”

“…Confining close-packed, functionalised molecules within parallel channels allows one to address a number of interesting solid-state properties, especially when the guests themselves are aligned co-parallel within the cavities. [9] More recent examples include a model system for light-harvesting by migration of photonic energy along aligned dye molecules in a zeolite, [10] the demonstration of an organic laser using a zeolite host, [11] and the tuning of spontaneous polarity formation in organic channel-type inclusion compounds driven by a Markov process. [12] Because many of the chromophores providing photonic and nonlinear optical (NLO) properties can be made from rodshaped molecules, the design of disc-(oblate-top) or rod-(prolate-top) shaped host molecules is of interest for assembling corresponding guest and host compounds into channeltype supramolecular structures.…”

Low-frequency vibrational control of crystal growth from melt

“…EO effect), recent interest focused on t11e packing of NLO molecules along pmallel chm1nels of inclusion type lattices [ 4]. When compared to other host materials [5], perhydroniphenylene (PHTP) worked out to be ideally suited [6,7] to include a vmiety of linemly shaped NLO entities of tl1e A-rr-D type (A, D: acceptor, donor group, respectively; rr: tlliophene, stilbene, polyphenyl, polyacetylene). SHG powder tests revealed tl1at PHTP-(A-rr-D) inclusion for111ation produces polm• materials at a yield of mound 75% tllat is 3 times lligher tl1m1 found for coiTesponding single component systems.…”

Helicale Koordinationspolymere mit großen chiralen Hohlräumen

“…Der Ersatz der entscheidenden C-H-Funktionalität durch eine Nitrogruppe und die damit verbundene sterische und chemische Verhinderung einer Kante-Kante-Stapelung führen zu einem weiteren interessanten, aber vollständig anderen supramolekularen Analogon von 1: Die Kristallstruktur von 2 besteht aus linearen Ketten, die sich unter Bildung einer trigonalen Architektur (Raumgruppe P3 1 ; a 11.2989 (5), c 17.5432(10) ; V 1936.6(2) 3 ) stapeln. Dagegen führte der Ersatz einer weniger entscheidenden C-H-Gruppe zur selben Architektur wie bei 1 a ± f: So weist 3 CÀH´´´p-Wechselwirkungen auf und kristallisiert mit einer fast identischen Struktur (auch in bezug auf die Hohlräume) wie der von 1 a ± f (Raumgruppe Einige Beobachtungen und Schluûfolgerungen der hier beschriebenen Ergebnisse möchten wir hervorheben: * Es wird immer deutlicher, daû chirale kristalline Architekturen und Hohlräume oder Kanäle [19,20] unter Verwen-dung der einfachsten achiralen molekularen Komponenten hergestellt werden können. Darüber hinaus induzieren die Eigenschaften der Hohlräume die Bildung chiraler Addukte aus achiralen Gastmolekülen.…”