Supramolecular self-assembly of structurally diversified ninhydrin-based molecules

doi:10.1016/j.molstruc.2020.129033

Journal of Molecular Structure

Volume 1224, 15 January 2021, 129033

https://doi.org/10.1016/j.molstruc.2020.129033 Get rights and content

Highlights

•
Potential of ninhydrin derivatives for tailoring diverse supramolecular architectures is unveiled.
•
Solid state structures of ninhydrin-acetamide adduct, ninhydrin-p-cresol adduct and N-inserted ninhydrin derivative are analyzed.
•
First cocrystal of ninhydrin family with 2-aminopyridine is disclosed.
•
SEM images indicate the surface morphology is greatly influenced by substitution of ninhydrin core.

Abstract

The present work discloses the self-assembly behaviour of differently substituted ninhydrin-based compounds in the solid state for the first time. Ninhydrin core with tunable functionalities generates varied noncovalent interactions leading to different supramolecular assembly. Single crystal X-ray diffraction study revealed that, ninhydrin-acetamide adduct 1 self-assembled to form corrugated sheet structure, whereas ninhydrin-p-cresol adduct 2 (cis dihydroxy hemiketal) containing water of crystallization was found to form water-mediated supramolecular helical architecture. On the other hand, easily achievable N-inserted ninhydrin derivative 3 derived from adduct 2 and o-aminophenol adopted helical arrangement in the crystalline state. Interestingly, novel cocrystal 4 obtained from adduct 2 was found to display helical motif through well directed hydrogen bonding with 2-aminopyridine. The supramolecular diversity arising due to the change in substitution of ninhydrin core structure was also reflected in scanning electron microscopy images.

Graphical abstract

Introduction

Self-assembled supramolecular structures are ubiquitous in biological systems and biomaterials [1], [2], [3], [4], [5], [6]. These types of structures are governed by non-covalent interactions like hydrogen bonding, hydrophobic and hydrophilic interaction, π-stacking, interaction between ionic groups [7], [8], [9], [10], [11], [12], [13], [14]. In recent decades, wisely designed molecular building blocks have attracted intensive attention due to their unique supramolecular architecture, elegant morphology as well as their potential applications in diverse fields [1], [15], [16]. To date, extensive efforts have been invested for constructing such superstructures based on macromolecules, inorganic compounds and MOFs [17], [18], [19], [20], [21], [22], [23]. However, investigation of self-assembly process employing small organic molecules is relatively rare in supramolecular chemistry and crystal engineering [24], [25], [26], [27], [28]. For example, Khavasi et al. reported the formation of sheet structure involving halogen substituted naphthamide and quinoline carboxamide derivatives [24]. Helical structures employing small organic molecule (3,4,9,10-perylenetetracarboxylic dianhydride) was demonstrated by Zhou and co-workers [27]. Recently, Sharma group successfully disclosed propensity of prolamide thymidine/uridine analogues towards typical helical motif [28]. Therefore, it remains a challenging and continuing task to accomplish small organic scaffolds exhibiting distinctive self-assembly behaviour.

On the other hand, self-assembly of cocrystals is of great interest due to their fascinating structural pattern as well as potential applications in medicinal chemistry, material science and host-guest chemistry [29], [30], [31], [32], [33], [34]. Cocrystals are usually designed and synthesized in the form of crystalline solid comprising of two or more organic entities based on noncovalent interactions [35], [36], [37], [38], [39], [40], [41]. among various type of cocrystal system, carboxylic acid-pyridine combinations are well established due to their potential application in drug discovery research [38], [39], [40], [41]. However, reports on cocrystal exploiting aliphatic hydroxyl groups have rarely been witnessed [42]. In this context, ninhydrin-adducts containing hydroxyl groups with cis orientation may serve as promising candidate to assemble suitable pyridine system.

Ninhydrin (1,2,3-Indanetrione monohydrate) is a stable organic compound bearing gem dihydroxy groups at C-2 position which is flanked by two carbonyl groups. To date, much of the ninhydrin related research have been directed towards organic synthesis, traditional peptide chemistry and forensic sciences [43], [44], [45], [46], [47]. However, self-assembly study of ninhydrin derivatives remains under-investigated. A study by Medrud on the structure of ninhydrin revealed that the molecules of ninhydrin in the crystalline state are connected in layers by well directed hydrogen bonding [48]. This typical structural pattern could be diversified by introducing suitable atoms/groups in ninhydrin core and thereby creating opportunity for interesting self-assembling propensity as well as surface morphology. As a part of our ongoing research [49], [50], [51], [52], herein, we unveil the self-assembly behaviour and morphological studies of simple ninhydrin-derivatives by modulating the substitution pattern.

Section snippets

Materials and physical measurements

All chemicals were purchased from commercial sources and used as received without further purification. Melting points were determined in open glass capillary and were uncorrected. TLC analyses were run on a Merck Kieselgel 60 PF₂₅₄ aluminium sheets. The spots were detected with UV light as well as with iodine. IR spectra were examined in KBr disc on a Perkin Elmer-L120–000A spectrometer. Proton magnetic resonance (¹H NMR) spectra were recorded on a Bruker Avance 300 and 500 spectrometer in

Synthesis

Molecular geometry, position of hydrogen bonding groups as well as π-functionalities have been utilized as powerful tool to regulate self-assembly habits in the solid state [57], [58]. With this in mind, ninhydrin molecule (which is a strong electrophile) has been chemically modified to generate variable network of non-covalent interactions. The synthetic pathway of compounds 1–4 is shown in Scheme 1. Ninhydrin-acetamide adduct 1 was obtained at room temperature from an aqueous solution of

Conclusions

This work demonstrates, for the first time, the potential of ninhydrin derivatives for tailoring diverse supramolecular architectures in the solid state. Different functional substitutes with varied intermolecular contact features have been introduced into the ninhydrin core to generate additional noncovalent interactions and assembly properties. Single crystal XRD revealed that adduct of ninhydrin and acetamide self-assembled to adopt corrugated sheet structure. Ninhydrin-p-cresol adduct

CRediT authorship contribution statement

Suven Das: Conceptualization, Writing - original draft, Writing - review & editing. Purak Das: Writing - original draft, Data curation, Resources. Suvendu Maity: Data curation, Formal analysis, Software. Prasanta Ghosh: Data curation, Formal analysis, Software. Arpita Dutta: Writing - original draft, Formal analysis.

Declaration of Competing Interest

There are no conflicts to declare.

Acknowledgements

We gratefully acknowledge laboratory facilities of R. B. C. College for Women, Naihati. PD is thankful to SERB (DST), India for a fellowship [No. TAR/2018/000228]. We thank Dr. Bijan K. Paul, Department of Chemistry, Mahadevananda Mahavidyalaya, India for helpful discussion.

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Supramolecular self-assembly of structurally diversified ninhydrin-based molecules

Highlights

Abstract

Graphical abstract

Introduction

Section snippets

Materials and physical measurements

Synthesis

Conclusions

CRediT authorship contribution statement

Declaration of Competing Interest

Acknowledgements

Org. Electron.

J. Mol. Liq.

Drug Discov. Today

J. Mol. Struct.

Tetrahedron

J. Mol. Struct.

J. Mol. Struct.

Chem. Rev.

Proc. Natl. Acad. Sci. U.S.A

Nature

J. Am. Chem. Soc

Proc. Natl. Acad. Sci. U.S.A.

Proc. Natl. Acad. Sci. U.S.A.

Angew. Chem. Int. Ed.

Acc. Chem. Res.

J. Am. Chem. Soc.

Helv. Chim. Acta

J. Am. Chem. Soc.

Angew. Chem. Int. Ed.

Chem. Rev.

Chem. Rev.

J. Am. Chem. Soc.

Chem. Commun

Chem. Rev.

Angew. Chem. Int. Ed.

Cryst. Growth Des.

CrystEngComm

Angew. Chem. Int. Ed.

CrystEngComm