Solid-state architecture

The previous structural and sorption studies of MOFs are all based on the discrete Zn40(C02)6 SBU. Recent development has demonstrated that rod-shaped metal-carboxylate SBUs can also give rise to a variety of stable solid-state architectures and permanent porosity. Three illustrative examples are presented below. 

Lehn reported the synthesis and solid-state architecture of chiral 2,5-diazabicyclo[2.2.2]octane-3,6-dione. The racemic material adopted an infinite chain of alternating (+) and (-) units, whereas the single enantiomer formed a cyclic tetrameric structure (Fig. 11.14) [49]. 

Williams JH. The molecular electric quadrupole moment and solid-state architecture. Acc Chem Res 1993 26 593-598. 

Homopolynuclear copper acetylacetonate complexes containing phen or bipy bridges play an important role in sustaining supramolecular solid-state architectures. A group of... 

Clyburne, J.A.C. Hamilton, T. Jenkins. H.A. The molecular quadrupole moment Solid state architectures containing organic and organometallic molecules. Cryst. Eng. 2001. 4. 1-9. 

Roesky, H.W. Andruh. M. The interplay of coordinative, hydrogen bonding and n-n stacking interactions in sustaining supramolecular solid-state architectures. A study case of bis(4-pyridyl)-and bis(4-pyridyl-N-oxide) tectons. Coord. Chem. Rev. 2003. 236. 91. and references therein. 

Alternate LB layers. The LB technique provides the possibility for alternate layers of different sets of molecules, which are forced to come in contact in the polar plane. The only requirement is that the attraction between the polar head is greater than the attraction with water. This powerful procedure allows a great many combinations for solid-state architecture (non centro-symmetric crystals, hetero duners, solid-state synthesis, molecular recognition). 

However, today, at the very early stage of this solid-state architecture, some examples have already been described, where rather simple molecules are manipulated by the help of the LB technique, combined with in situ chemistry. 

Mn(CO)3(jU3-OH) 4 2H2NCH2CH2CH2NH2] , 79, is depicted in Figure 5.3. The hydroxo complex 78 (M = Mn) can be considered a prototypal building block in the design of organometallic solid-state architecture. It is interesting to note that no short intermolecular contacts have been found in the crystal structure of the unsolvated compound [44]. 

Kolb U, Buscher K, Helm CA, Lindner A, Thunemann AF, Menzel M, Higuchi M, Kurth DG (2006) The solid-state architecture of a metallosupramolecular polyelectrolyte. Proc Natl Acad Sci U S A 103 10202-10206. doi 10.1073/pnas.0601092103... 

Zerkowski, J. A., and Whitesides, G. M. (1994) Steric Control of Secondary, Solid-State Architecture in 1 1 Complexes of Melamines and Barbiturates That Crystallize as Crinkled Tapes, J. Am. Chem. Soc. 116, 4298-4304. 

Zhang and coworkers [95] reported an intruiguing solid state architecture in which two calix[8]arene macrocycles in a double-cone conformation were coordinated to a [Ce s] octahedron while ligated DMF molecules were inside the cavities (Fig. 7.29) [95]. 

Finally, entirely new generations of products could be envisioned that use molecules for the central processing and memory components of top-of-the-line computers in configurations that bear little relation to present-day solid-state architectures. There are high prospects for using molecular electronics in this venue however, commercially relevant delivery times for such systems are minimally a decade away. Specific possibilities will be considered in Chapter 5. 

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