Topologic Equivalents of Coronands, Cryptands and Their Inclusion Complexes: Synthesis, Structure and Properties of {2}‐Metallacryptands and {2}‐Metallacryptates

Saalfrank, Rolf W.; Dresel, A.; Seitz, Verena; Trümmer, Stefan; Hampel, Frank; Teichert, Markus; Stalke, Dietmar; Stadler, Christian; Daub, Jörg; Schünemann, Volker; Trautwein, Alfred X.

doi:10.1002/chem.19970031222

Cited by 92 publications

(50 citation statements)

References 49 publications

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“…Examples are crystallised from dichloromethane by diffusion of a mixture the well-known crown ethers, cryptands, spherands and of diethyl ether and hexanes (1:5). The X-ray diffraction their inclusion complexes [1] [2] , along with the corresponding analysis of these crystals proved the formation of a stronmetallatopomers, which are easily accessible by self- [6] [7] [8] (Scheme 1). The encapsulated strontium dication does not lie perResults and Discussion fectly on the ironϪiron axis (FeϪSrϪFe 174.39°).…”

Section: Introductionmentioning

confidence: 99%

Self-Assembly of {2}-Metallacryptands and {2}-Metallacryptates

Saalfrank¹,

Seitz

Caulder

et al. 1998

Eur. J. Inorg. Chem.

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Section: Introductionmentioning

confidence: 99%

Self-Assembly of {2}-Metallacryptands and {2}-Metallacryptates

Saalfrank¹,

Seitz

Caulder

et al. 1998

Eur. J. Inorg. Chem.

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“…On each face of the imaginary tetrahedron constituted by the four magnesium ions, three oxygen atoms are in ideal positions to bind an ammonium ion through three hydrogen bonds. [6] Recently we pointed out the structural analogy between the classical crown ethers, cryptands, spherands and their inclusion complexes, and the class of topologically analogous metalla-crown ethers (MC), [9,10] metalla-cryptands, [2] and metalla-spherands [4] and their inclusion compounds. If one applies the knowledge about crown ethers to the chemistry of metalla-crown ethers, then the complexation of different sized cations by metalla-crown ethers should lead to metallacoronates of different structures.…”

Section: Resultsmentioning

confidence: 99%

“…Therefore metal-directed multicomponent self-assembly is currently attracting great attention as a strategy for the synthesis of polynuclear metal complexes, in order to develop new materials with novel properties and structural features. [1] Over the last few years we have devised and described a versatile procedure for the synthesis of numerous bis-, [2] tris-, [3] tetra-, [4] hexa- [5] and octanuclear [5,6] chelate complexes. The metal-directed self-assembly of polydentate ligands with transition metal ions leads to metalla-crown ethers, [7] which are topological analogues of crown ethers.…”

Section: Introductionmentioning

confidence: 99%

Metal-Directed Formation of Tetra-, Hexa-, Octa-, and Nonanuclear Complexes of Magnesium, Calcium, Manganese, Copper, and Cadmium

et al. 1998

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“…The treatment of the diketone ligand 30 with Fe III in the presence of KH as a base produces the cryptate 31 in good yield (Figure 31). 36 This indicates that the first complexation with Fe III fixes the molecular structure favorable for the second reaction. Metal cryptates 33 are also generated from [TiO(acac) 2 ] and the podand 32 bearing catechol moieties at the ends of the chains by template assistance of the alkali metal ions with a suitable size for the cryptand cavity ( Figure 32).…”

Section: ¹1mentioning

confidence: 97%

Construction of Cooperative and Responsive Supramolecular Systems for Molecular Functional Modulation

Nabeshima¹

2010

Bulletin of the Chemical Society of Japan

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The transfer and modulation of the molecular information are necessary processes for cooperative and responsive molecular functions. When functional molecules are responsive to external (intermolecular) as well as internal (intramolecular) stimuli, the molecules exhibit cooperative functions in principle. We have developed a variety of cooperative and responsive supramolecular systems created on the basis of new concepts for the molecular design of sophisticated functional systems. The first uses pseudomacrocycles including pseudocrown ether, pseudocryptands, and pseudocyclophanes as novel frameworks for response functions by utilizing a metal ion as an effector. The second utilizes a molecular gate responding to an external signal. The gate is opened and closed by a signal achieving perfect onoff switching for guest recognition. The next exploits metal-accumulated molecular systems bearing oligo C=N moieties as a binding site for metal ions. This strategy is remarkably useful for producing new binding sites by structural fixation of multi-metal complexes and to modulate properties of metal ions. Other cooperative molecular assembling systems for host generation are also demonstrated in this account. Metallo-frameworks and self-assembled metallo-systems recently developed in our laboratories, which have high potential for synergistic molecular functions, are discussed. Future cooperative functional systems will be widely applicable as multi-responsive multi-functional supramolecules, molecular functional cascades for successive molecular functions and function amplification. Study of cooperative and responsive molecular systems may lead to more general fields such as complex systems science, which is at the interface of chemistry, physics, biology, and mathematics.Responsive regulation of molecular functions requires information transfer at the molecular level (Figure 1).1 Receiving and releasing substances, such as molecules, metal ions, electrons, and photons, is regarded as an information transfer event. The properties of the substances, such as chirality, order, spatial arrangement, and the combination of atomic and molecular arrays can also provide information to control functions. These regulation systems are referred to as molecular systems responding to external stimuli and are also closely related to cooperative functional systems. Intramolecular and/ or intermolecular interactions play a very important role in cooperative functions. In other words, intramolecular and/or intermolecular communication between different parts of the molecules is necessary to generate the observed phenomena, which are very important and interesting with respect to molecular property memory and amplification of molecular functions. Cooperative systems generally consist of two parts, a receptor site for the stimulus and an active site for the function.

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Topologic Equivalents of Coronands, Cryptands and Their Inclusion Complexes: Synthesis, Structure and Properties of {2}‐Metallacryptands and {2}‐Metallacryptates

Abstract: Abstract:The synthesis and structural characterisation of two dinuclear iron(n1) complexes are reported.

Cited by 92 publications

References 49 publications

Self-Assembly of {2}-Metallacryptands and {2}-Metallacryptates

Self-Assembly of {2}-Metallacryptands and {2}-Metallacryptates

Metal-Directed Formation of Tetra-, Hexa-, Octa-, and Nonanuclear Complexes of Magnesium, Calcium, Manganese, Copper, and Cadmium

Construction of Cooperative and Responsive Supramolecular Systems for Molecular Functional Modulation

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