The addition of pyridine‐3‐carboxylic acid (3‐PyCOOH), (E)‐3‐(pyridin‐3‐yl)acrylic acid (3‐PyCH=CHCOOH), or 3‐(pyridin‐4‐yl)benzoic acid (3‐PyPhCOOH) to the Lewis acidic [Cu(dppf)(NCMe)2][BF4]·2MeCN·2H2O [1·2MeCN·2H2O, dppf = 1,1′‐bis(diphenylphosphanyl)ferrocene] in the presence of NEt3 afforded the complexes [Cu2(dppf)2(3‐PyCOO)2]·3CHCl3 (2·3CHCl3), [Cu2(dppf)2(3‐PyCH=CHCOO)2]·CH2Cl2·C6H14 (3·CH2Cl2·C6H14), and [Cu2(dppf)2(3‐PyPhCOO)2]·CH2Cl2 (4·CH2Cl2) with a common metallomacrocycle core and doubly bridging pyridine–carboxylate ligands as spacers. These dinuclear complexes have been structurally characterized by single‐crystal X‐ray crystallography, and their emission activities have been studied.
The use of simple self-assembly methods to direct or engineer porosity or channels of desirable functionality is a major challenge in the field of metal-organic frameworks. We herein report a series of frameworks by modifying square ring structure of [{Cu2(5-dmpy)2(L1)2(H2O)(MeOH)}2{ClO4}4]·4MeOH (1·4MeOH, 5-dmpy = 5,5'-dimethyl-2,2'-bipyridine, HL1 = 4-pyridinecarboxylic acid). Use of pyridyl carboxylates as directional spacers in bipyridyl chelated Cu(II) system led to the growth of square unit into other configurations, namely, square ring, square chain, and square tunnel. Another remarkable characteristic is that the novel use of two isomers of pyridinyl-acrylic acid directs selectively to two different extreme tubular forms-aligned stacking of discrete hexagonal rings and crack-free one-dimensional continuum polymers. This provides a unique example of two extreme forms of copper nanotubes from two isomeric spacers. All of the reactions are performed in a one-pot self-assembly process at room temperature, while the topological selectivity is exclusively determined by the skeletal characteristics of the spacers.
As molecular synthesis advances, we are beginning to learn control of not only the chemical reactivity (and function) of molecules, but also of their interactions with other molecules. It is this basic idea that has led to the current explosion of supramolecular science and engineering. Parallel to this development, chemists have been actively pursuing the design of very large molecules using basic molecular building blocks. Herein, we review the general development of supramolecular chemistry and particularly of two new branches: supramolecular coordination complexes (SCCs) and metal organic frameworks (MOFs). These two fields are discussed in detail with typical examples to illustrate what is now possible and what challenges lie ahead for tomorrow's molecular artisans.
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