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A New Organic Nanoporous Architecture: Dumb‐Bell‐Shaped Molecules with Guests in Parallel Channels
Author(s) -
Müller Torsten,
Hulliger Jürg,
Seichter Wilhelm,
Weber Edwin,
Weber Thomas,
Wübbenhorst Michael
Publication year - 2000
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/(sici)1521-3765(20000103)6:1<54::aid-chem54>3.0.co;2-y
Subject(s) - supramolecular chemistry , molecule , chromophore , crystallography , chemistry , polarity (international relations) , nanoporous , crystal (programming language) , dipole , crystallization , chemical physics , materials science , nanotechnology , stereochemistry , crystal structure , photochemistry , organic chemistry , biochemistry , computer science , programming language , cell
A new type of dumb‐bell‐shaped host molecule ( 6 ‐ 8 ) has been synthesised, of which 1,8‐bis((1)‐adamantyl)‐1,3,5,7‐octatetrayne ( 8 =BAOT) forms an open porous architecture when cocrystallised with a number of typical solvent molecules. Adamantyl substituents attached to a tetraalkyne spacer build up the walls of parallel channels wherein guest molecules are aligned. Surprisingly, the tetraalkyne unit is significantly bent. Desolvation experiments provide evidence for a reversible inclusion of guests. In the case of the inclusion of 2‐butanone, a partial substitution by symmetrical and asymmetrical long‐chain chromophores during crystallisation was possible. Stained crystals showed optical frequency doubling. The crystal structure analysis revealed a centric space group, although considerable translational and orientational disorder was present. Application of scanning pyroelectric microscopy revealed that the growth of inclusion compounds with 2‐butanone produced polar ordering of guest molecules, which were aligned in two macro‐domains of opposing polarity. The resulting orientation of the carbonyl dipoles is in agreement with the theoretical prediction of a Markov model of spontaneous polarity formation based on molecular recognition processes on growing crystal faces. The present case represents a new example of a property‐driven supramolecular synthesis.