Cobaltocenium based receptors

We recently incorporated the ruthenium(II) bipyridyl moiety into acyclic, macrocyclic, and lower rim caUx[4Jarene structural frameworks to produce a new class of anion receptor capable of optical and electrochemical sensing (226, 253. 254). Stability constant determinations in DMSO using H NMR titration techniques demonstrated that these acyclic receptors (131 and 132) form strong complexes with chloride and dihydrogen phosphate anions (stronger than with analogous monopositive cobaltocenium based receptors). The ruthenium ion is dipositive and hence the electrostatic interactions are particularly favorable. The 4,4 -substituted ruthenium bipyridyls were observed to bind anions more... 

A macrocyclic receptor (100) has also recently been prepared and its crystal structure was elucidated (220). In comparison with its acyclic analogue 101, an anion macrocyclic effect was observed, the stability constants for chloride complex formation [in DMSO] being K = 250 M (100) and K = 20 M (101). Receptor 102 was shown to act as a switchable cobaltocenium based chloridebinding host (221). The free receptor binds chloride anions, but on the addition of potassium ions, the binding is switched off. This effect is probably due to the ability of the potassium ion to form a sandwich complex with the two crown ether substituents, sterically hindering the anion-binding site. 

Cobaltocenium based systems have therefore proved very versatile in the field of anion coordination chemistry. The role of the cobaltocenium unit is to enhance interaction with the bound anion and to function as a sensing unit. The structure of the receptor can then be controlled by simple organic manipulations of the Cp groups. In this manner, novel anion selectivity can readily be incorporated into these receptors. 

Ferrocene units appended with secondary amides have also been used for anion recognition (113-115) (231). Being neutral, unlike cobaltocenium based systems, these receptors have no inherent electrostatic attraction making the NMR stability constants much lower in magnitude than for the analogous cobaltocenium systems. Electrostatic interactions can, however, be switched on by oxidation of ferrocene to ferrocenium and consequently these molecules show interesting electrochemical effects and have a potential as amperometric anion sensors. Of interest to this development of sensor technology were the novel results of electrochemical competition experiments. These results demonstrated... 

The common reporter groups cobaltocenium and ferrocene have not frequently been used in optical anion sensing, since these chromophores are generally insensitive to anion binding. However, metaUocene-based receptors... 

Anion receptors incorporating cobaltocenium have been studied extensively due to the combination of an accessible redox couple and potential favourable electrostatic interactions of the cationic organometallic metallocene complex with anions. The first anion receptor based on this species was reported by Beer and co-workers in 1989 [6]. The macrocyclic bis-cobaltocenium receptor 1 was shown to bind (via electrostatic interaction) and to electro chemically sense bromide in acetonitrile solvent media. 

The accessible ferrocene/ferrocenium redox couple of ferrocene has led to its frequent use in electrochemical anion sensors. The chemical and structural similarity between ferrocene and cobaltocenium has meant that receptors based on these complexes often share the same design. The most relevant difference is that the ferrocene derivatives are neutral (until oxidised to ferrocenium),have no inherent electrostatic interaction with anions and therefore their complexes with anions exhibit lower stability constants. 

Receptor 93 incorporates a zinc porphyrin backbone with four ferrocene amides [65]. This shares the design of the cobaltocenium receptor 4, except that now a zinc atom occupies the centre of the porphyrin. The Lewis acid metal centre provides an additional binding site for anion recognition. In dichloro-methane solution no significant anion-induced shifts in the lH NMR signals of the amide protons were seen in the free-base precursor of 93, whereas the... 

The first ester functionalized cobaltocenium receptor (74) developed by us in 1989, was based solely on electrostatic interactions (as discussed earlier) (9, 186). It was therefore decided to append the cobaltocenium moiety with secondary amide functionalized arms . In this manner, the receptors became more resistant to hydrolysis (a recurrent problem with ester-based systems), and also incorporated neutral hydrogen-bond donors capable of coordinating anions. [An interaction between a secondary amide (acetamide) and the bromide anion was physically investigated (by IR spectroscopy) as long ago as 1961 (211)]. We made the first report of this novel type of receptor (91 and 92) in 1992 (212), which was, in fact, the first class of inorganic anion receptor that incorporated hydrogen-bonding functionalities. 

We have also synthesized a ditopic cobaltocenium host based on a ca-lix[4]arene framework (103) and reported its crystal structure (Fig. 13) (219, 222). This receptor was shown to form extremely stable 1 1 anion complexes in polar DMSO solutions as well as with the adipate anion in acetone. 

Another class of mixed-metal anion receptors has been investigated which possess redox reporter groups based on two different metal complexes. This enables the quahtative comparison of their comparative anion-sensing abih-ties. Macrocycles 35 and 36 combine the Ru (bpy)3 moiety with a bridging ferrocene or cobaltocenium imit [29]. Electrochemical experiments in acetonitrile solution revealed that the Ru VRu redox potential was insensitive to anion binding, whereas the ferrocene/ferrocenium (in 35) and cobal-tocene/cobaltocenium (in 36) redox couples were shifted cathodically (by 60 mV and 110 mV respectively with chloride). However, the first reduction of Ru°(bpy)3, a Hgand-centred process based on the amide substituted bipyridyl, was also found to imdergo an anion induced cathodic shift (40 mV and 90 mV with chloride for 35 and 36, respectively). 

The cobaltocenium moiety was studied extensively in the context of redox-responsive anion receptors. " The first class of anion receptor based on this system was reported by Beer and Keefe in 1989. The ester functionalized hi 5-cobaltocenium maeroeyelie Reeeptor 1 bound and eleetroehemieally sensed bromide in acetonitrile via favorable electrostatic interactions. 

Studies of synthetic porphyrin-based anion receptors should form the basis for more effective sensors. Metallocene-substituted porphyrins examined by Beer and coworkers have proven successful in the solution-phase binding of ions such as chloride, bromide and nitrate." The cobaltocenium-substituted and ferrocene-substituted porphyrins (Figure 134) bind ions in solution, as shown by H NMR and electrochemical studies. The latter measurements reveal that the porphyrin and ferrocene redox... 

A new class of ferrocene (also cobaltocenium) receptors which sense anions both spectrally and electrochemically, is based upon attachment of metallocene moieties to a porphyrin skeleton. The porphyrin fragment can be simultaneously complexed by zinc [120]. 

Another variety is the ester type of receptors, containing carboxycobaltocenium units esterified with various diphenols, 72 and 73, which introduce aromatic spacers [122]. Such compounds accept Br guests and shift the cobaltocenium reduction wave towards more negative potentials. In this instance anion recognition and fixation seem to be based simply on electrostatic interactions. 

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