Dataset Information

Luminescent Anion Sensing by Transition-Metal Dipyridylbenzene Complexes Incorporated into Acyclic, Macrocyclic and Interlocked Hosts.

ABSTRACT: A series of novel acyclic, macrocyclic and mechanically interlocked luminescent anion sensors have been prepared by incorporation of the isophthalamide motif into dipyridylbenzene to obtain cyclometallated complexes of platinum(II) and ruthenium(II). Both the acyclic and macrocyclic derivatives 7⋅Pt, 7⋅Ru⋅PF6 , 10⋅Pt and 10⋅Ru⋅PF6 are effective sensors for a range of halides and oxoanions. The near-infra red emitting ruthenium congeners exhibited an increased binding strength compared to platinum due to the cationic charge and thus additional electrostatic interactions. Intramolecular hydrogen-bonding between the dipyridylbenzene ligand and the amide carbonyls increases the preorganisation of both acyclic and macrocyclic metal derivatives resulting in no discernible macrocyclic effect. Interlocked analogues were also prepared, and preliminary luminescent chloride anion spectrometric titrations with 12⋅Ru⋅(PF6 )2 demonstrate a marked increase in halide binding affinity due to the complementary chloride binding pocket of the [2]rotaxane. 1 H NMR binding titrations indicate the interlocked dicationic receptor is capable of chloride recognition even in competitive 30 % aqueous mixtures.

SUBMITTER: Knighton RC

PROVIDER: S-EPMC7216984 | biostudies-literature | 2020 Apr

REPOSITORIES: biostudies-literature

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Luminescent Anion Sensing by Transition-Metal Dipyridylbenzene Complexes Incorporated into Acyclic, Macrocyclic and Interlocked Hosts.

Knighton Richard C RC Dapin Sophie S Beer Paul D PD

Chemistry (Weinheim an der Bergstrasse, Germany) 20200401 23

A series of novel acyclic, macrocyclic and mechanically interlocked luminescent anion sensors have been prepared by incorporation of the isophthalamide motif into dipyridylbenzene to obtain cyclometallated complexes of platinum(II) and ruthenium(II). Both the acyclic and macrocyclic derivatives 7⋅Pt, 7⋅Ru⋅PF<sub>6</sub> , 10⋅Pt and 10⋅Ru⋅PF<sub>6</sub> are effective sensors for a range of halides and oxoanions. The near-infra red emitting ruthenium congeners exhibited an increased binding streng ...[more]

PMID: 32130744

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Project description:The Eu(III) complex of (1S,4S,7S,10S)-1,4,7,10-tetrakis(2-hydroxypropyl)-1,4,7,10-tetraazacyclododecane (S-THP) is studied as a sensor for biologically relevant anions. Anion interactions produce changes in the luminescence emission spectrum of the Eu(III) complex, in the (1)H NMR spectrum, and correspondingly, in the PARACEST spectrum of the complex (PARACEST = paramagnetic chemical exchange saturation transfer). Direct excitation spectroscopy and luminescence lifetime studies of Eu(S-THP) give information about the speciation and nature of anion interactions including carbonate, acetate, lactate, citrate, phosphate, and methylphosphate at pH 7.2. Data is consistent with the formation of both innersphere and outersphere complexes of Eu(S-THP) with acetate, lactate, and carbonate. These anions have weak dissociation constants that range from 19 to 38 mM. Citrate binding to Eu(S-THP) is predominantly innersphere with a dissociation constant of 17 μM. Luminescence emission peak changes upon addition of anion to Eu(S-THP) show that there are two distinct binding events for phosphate and methylphosphate with dissociation constants of 0.3 mM and 3.0 mM for phosphate and 0.6 mM and 9.8 mM for methyl phosphate. Eu(THPC) contains an appended carbostyril derivative as an antenna to sensitize Eu(III) luminescence. Eu(THPC) binds phosphate and citrate with dissociation constants that are 10-fold less than that of the Eu(S-THP) parent, suggesting that functionalization through a pendent group disrupts the anion binding site. Eu(S-THP) functions as an anion responsive PARACEST agent through exchange of the alcohol protons with bulk water. The alcohol proton resonances of Eu(S-THP) shift downfield in the presence of acetate, lactate, citrate, and methylphosphate, giving rise to distinct PARACEST peaks. In contrast, phosphate binds to Eu(S-THP) to suppress the PARACEST alcohol OH peak and carbonate does not markedly change the alcohol peak at 5 mM Eu(S-THP), 15 mM carbonate at pH 6.5 or 7.2. This work shows that the Eu(S-THP) complex has unique selectivity toward binding of biologically relevant anions and that anion binding results in changes in both the luminescence and the PARACEST spectra of the complex.

Dataset Information

Luminescent Anion Sensing by Transition-Metal Dipyridylbenzene Complexes Incorporated into Acyclic, Macrocyclic and Interlocked Hosts.

Publications

Luminescent Anion Sensing by Transition-Metal Dipyridylbenzene Complexes Incorporated into Acyclic, Macrocyclic and Interlocked Hosts.

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