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Binding Properties of a Dinuclear Zinc(II) Salen-Type Molecular Tweezer with a Flexible Spacer in the Formation of Lewis Acid-Base Adducts with Diamines

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Binding Properties of a Dinuclear Zinc(II) Salen-Type Molecular Tweezer with a Flexible Spacer in the Formation of Lewis Acid-Base Adducts with Diamines inorganics Article Binding Properties of a Dinuclear Zinc(II) Salen-Type Molecular Tweezer with a Flexible Spacer in the Formation of Lewis Acid-Base Adducts with Diamines Gabriella Munzi , Giuseppe Consiglio , Salvatore Failla and Santo Di Bella * Dipartimento di Scienze Chimiche, Università di Catania, I-95125 Catania, Italy; [email protected] (G.M.); [email protected] (G.C.); [email protected] (S.F.) * Correspondence: [email protected] Abstract: In this paper we report the binding properties, by combined 1H NMR, optical absorption, and fluorescence studies, of a molecular tweezer composed of two Zn(salen)-type Schiff-base units connected by a flexible spacer, towards a series of ditopic diamines having a strong Lewis basicity, with different chain length and rigidity. Except for the 1,2-diaminoethane, in all other cases the formation of stable 1:1 Lewis acid-base adducts with large binding constants is demonstrated. For a,w-aliphatic diamines, binding constants progressively increase with the increasing length of the alkyl chain, thanks to the flexible nature of the spacer and the parallel decreased conformational strain upon binding. Stable adducts are also found even for short diamines with rigid molecular structures. Given their preorganized structure, these latter species are not subjected to loss of degrees of freedom. The binding characteristics of the tweezer have been exploited for the colorimetric and fluorometric selective and sensitive detection of piperazine. Citation: Munzi, G.; Consiglio, G.; Failla, S.; Di Bella, S. Binding Keywords: zinc(II) complexes; Schiff-bases; molecular tweezers; Lewis acid-base adducts Properties of a Dinuclear Zinc(II) Salen-Type Molecular Tweezer with a Flexible Spacer in the Formation of Lewis Acid-Base Adducts with Diamines. Inorganics 2021, 9, 49. 1. Introduction https://doi.org/10.3390/ “Molecular tweezers” refer to bifunctional molecular receptors characterized by the inorganics9060049 presence of two binding sites connected with a more or less rigid spacer [1,2]. They have the ability to form complexes with a substrate molecule, resembling a tweezer holding an Academic Editor: Isabel Correia object. Depending on the nature of the binding sites and on the conformational rigidity of the spacer, they find various applications such as in molecular recognition [1,3], in- Received: 27 April 2021 cluding biomolecules [4–6], or fullerenes [7], enzyme inhibition or prevention of protein Accepted: 11 June 2021 aggregation [8–10], catalysis [11], switchable molecular tweezers [12,13], electrochemical Published: 16 June 2021 switches [14,15], and as building blocks for supramolecular nanostructures [16,17]. Various molecular tweezers have been synthesized as hosts for guest molecules. Publisher’s Note: MDPI stays neutral Among them, glycoluril- [1,2] or porphyrin-based [3] tweezers are those most studied. with regard to jurisdictional claims in The latter have been involved in various investigations for their ability to bind ditopic published maps and institutional affil- species, e.g., for configuration [18,19] and chirogenesis [20–23] studies, and for the devel- iations. opment of sensors targeting specific molecules [24], including chiral species [25,26]. More- over, the binding behavior with ditopic guests of different length and rigidities has also been explored [27–30]. Zn(salen)-type Schiff-base complexes have recently been investigated for their sensing Copyright: © 2021 by the authors. properties [31–33], mostly related to their Lewis acidic character [34]. These complexes Licensee MDPI, Basel, Switzerland. easily coordinate Lewis bases with formation of Lewis acid-base adducts, and this process This article is an open access article is accompanied by relevant changes of their spectroscopic properties. Among them, deriva- distributed under the terms and tives from the 2,3-diaminomaleonitrile, Zn(salmal) [35,36], are those mostly studied for conditions of the Creative Commons sensing a variety of Lewis bases [37–44]. Attribution (CC BY) license (https:// Recently, a dinuclear Zn(salmal) Schiff-base complex (1, Scheme1) whose units are con- creativecommons.org/licenses/by/ nected with a non-conjugated, flexible spacer, has been synthesized and characterized [45]. 4.0/). Inorganics 2021, 9, 49. https://doi.org/10.3390/inorganics9060049 https://www.mdpi.com/journal/inorganics Inorganics 2021, 9, 49 2 of 13 Inorganics 2021, 9, 49 2 of 13 Inorganics 2021, 9, 49 2 of 13 Recently, a dinuclear Zn(salmal) Schiff-base complex (1, Scheme 1)whose units are connectedRecently, with a nondinuclear-conjugated, Zn(salmal) flexible Schiff spacer,-base has complex been synthesized (1, Scheme and 1)whose characterized units are It[45].connected has Itbeen has beenwith found founda non that- conjugated,that in non-coordinating in non- flexiblecoordinating spacer, solvents solvents has1 beenis 1 stabilized issynthesized stabilized by thebyand the formationcharacterized formation of intramolecularof[45]. intramolecular It has been aggregates, foundaggregates, that which in which non hardly- coordinatinghardly deaggregate deaggregate solvents by by 1 addition additionis stabilized of of monotopicmonotopic by the formation LewisLewis bases.of intramolecular However, However, in inaggregates, the presence which of stronghardly ditopicdeaggregate Lewis by bases,bases, addition such of asasmonotopic diamines,diamines, Lewis thethe complexbases. However, easily deaggregates in the presence with formationof strong ofditopic 1:1 adducts, Lewis bases, thus acting such asas aadiamines, “molecular“molecular the tweezer”.complex easilyDeaggregation Deaggregation deaggregates is is accompanied with formation by relevantof 1:1 adducts, opticaloptical thus absorption acting as changes a “molecular and aa substantialtweezer”. Deaggregation enhancement of is theaccompanied fluorescence.fluorescence. by Therefore, relevant optic 1 hasal beenbeenabsorption investigatedinvestigated changes forfor and thethe a selectivesubstantial and enhancement sensitive detection of the ofof fluorescence. somesome biogenicbiogenic Therefore, diaminesdiamines 1 [[46].46has]. been investigated for the selective and sensitive detection of some biogenic diamines [46]. Scheme 1.1. StructureStructure ofof the the dinuclear dinuclear complex complex1. 1.As the dinuclear aggregate complex 1 acts as a “molecularScheme 1. tweezer”Structure upon of the deaggregation, dinuclear complex this is 1an.As unusual the dinuclear feature aggregatecompared complexTable 1. in1 actsthe for-as a mation“molecularAs of the Lewis tweezer” dinuclear acid-base upon aggregate adducts, deaggregation, complexit will not this 1beacts issubjected an as unusual a “molecular to binding feature as tweezer”compared a consequence upon Table deaggrega-of1. ain specific the for- tion,conformationmation this of is Lewis an of unusual the acid Lewis-base feature base. adducts, Rather, compared it will the not ability to be conventional subjected of the Lewis to tweezersbinding base to asbind characterized a consequence the aggregate by of bindingcoulda specific be sitesrelatedconformation kept to its separate basicity of the by Lewisand a spacer. to base. the stability Thus,Rather, starting theof the ability adduct. from of the the It Lewisis defined thus base interesting aggregate to bind tothe1 investigate, aggregate in the formation thecould fea- be ofturesrelated Lewis affecting to acid-base its basicitythe binding adducts, and interactionsto the it will stability not between be of subjectedthe thadduct.e aggregate to It binding is thus molecular interesting as a consequence tweezer to investigate 1, having of a specific athe flexi- fea- conformationbletures spacer, affecting and ofthethe the structurebinding Lewis interactions of base. the ditopic Rather, between Lewis the ability bases.the aggregate of the Lewis molecular base tweezer to bind 1 the, having aggregate a flexi- couldble spacer, be related and the to structure its basicity of the and ditopic to the Lewis stability bases. of the adduct. It is thus interesting to investigateThe aim the of features this work affecting is to study, the binding through interactions 1H NMR, between UV/vis, the and aggregate fluorescence molecular spec- tweezertroscopies,The1, aim havingthe of binding this a flexible work interactions spacer,is to study, and of thethroughthe structure tweezer 1H NMR, of1 thewith UV/vis, ditopic diamines Lewisand offluorescence bases.different chain spec- lengthtroscopies,The and aim rigidity, the of thisbinding to work better interactions is to understand study, through of theirthe tweezer1 LewisH NMR, acid 1 UV/vis,with-base diamines interactions. and fluorescence of d ifferent spectro- chain scopies,length and the bindingrigidity, interactionsto better understand of the tweezer their Lewis1 with acid diamines-base interactions. of different chain length and2. Results rigidity, and to Discussion better understand their Lewis acid-base interactions. 2. ResultsTo study and the Discussion binding of various diamines to the molecular tweezer 1, either ali- 2. Results and Discussion phatic,To alicyclic, study the and binding aromatic of diaminesvarious diamines were considered to the molecular (Scheme 2tweezer). In particular, 1, either theali- flexiblephatic,To studyprimaryalicyclic, the α bindingand,ω-aliphatic aromatic of various diamines, diamines diamines NH were2(CH to considered the2)nNH molecular2 (n = ( 2Scheme– tweezer12), were 2).1 ,Instudied, either particular, aliphatic, and
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