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Links New Chemistry A transition metal borylene complex
stabilized by a non- carbonyl
ligand set: formation by
spontaneous halide loss to give an
extremely short metal- -boron
bond (video). (work by David
Addy) |
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Sensors for Anions and Neutral
Molecules The
binding of anions by receptor molecules is an area of enormous research
interest, which is relevant to biological systems, and has widespread
applications, e.g. in catalysis and sensors. From the viewpoint of sensor
design, key features are selectivity (i.e. the recognition of the target
anion over possible contaminants) and signalling (i.e. the triggering of a
measurable response on anion binding). A wide variety of chemical strategies
have been employed to selectively bind anions, and we have been using group
13 based Lewis acids in this area – with the selectivity for the target anion
based either on the strength of the donor/acceptor bond formed (e.g. for
fluoride) or on the complementary geometry of the binding sites and target
anion (e.g. cyanide or acetate). Ongoing work is
centred on the design of novel multifunctional Lewis acids and mixed Lewis
acid/base systems for the selective detection of fluoride (and its conjugate
acid HF), together with the exploitation of such receptors in the sensing of
fluorinated chemical warfare agents (CWAs). Key receptor design principles
are (i) the known selectivity of fluoride binding by boronic esters; and (ii)
electrochemical, colorimetric or fluorescence based reporting (e.g. utilizing
ferrocene units, Fc). A further target is the selective sensing of cyanide
(or hydrogen cyanide) in the presence of potentially competitive anions (e.g.
halides).
Key future targets
with a view to device construction are improvements in sensitivity (i.e.
lower detection limits) and kinetics of response. Two approaches are
currently being appraised: (i) the incorporation of suitable redox-matched
dyes for fast, sensitive colorimetric sensing and (ii) the development of
catalytic sensors. The latter approach relies on identifying host/guest
complexes formed between the receptor and the target analyte which will
catalyze an orthogonal reaction. Our approach utilizes electron transfer
chemistry as the basis for catalysis, e.g. of a dye bleaching reaction. |
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Further Information Sensors Figures (left)
Crystal structure of a cyanide receptor based on a tolan backbone. (centre) Ferrocene-functionalized Lewis acids offer electrochemical and/or colorimetric sensing platforms. See: Dalton 2006, 3660
& 2007, 3486. (right) Electrochemical response to anion binding (here a ca. 500 mV shift on addition of cyanide). See: Angew.
Chem., Int. Ed. 2005, 44, 3606. New chemistry (video) A
1,2-difunctionalized ferrocene based Lewis acid. Click here. |