From construction to application of a new generation of interlocked molecules composed of heteroditopic wheels.

Over the last few decades, research on mechanically interlocked molecules has significantly evolved owing to their unique structural features and interesting properties. A substantial percentage of the reported works have focused on the synthetic strategies, leading to the preparation of functional MIMs for their applications in the chemical, materials, and biomedical sciences. Importantly, various macrocyclic wheels with specific heteroditopicity (including phenanthroline, amide, amine, oxy-ether, isophthalamide, calixarene and triazole) and threading axles (bipyridine, phenanthroline, pyridinium, triazolium, etc.) have been designed to synthesize targeted multifunctional mononuclear/multinuclear pseudorotaxanes, rotaxanes and catenanes. The structural uniqueness of these interlocked systems is advantageous owing to the presence of mechanical bonds with specific three-dimensional cavities. Furthermore, their multi-functionalities and preorganised structural entities exhibit a high potential for versatile applications, like switching, shuttling, dynamic properties, recognition and sensing. In this feature article, we describe some of the most recent advances in the construction and chemical behaviour of a new generation of interlocked molecules, primarily focusing on heteroditopic wheels and their applications in different directions of the modern research area. Furthermore, we outline the future prospects and significant perspectives of the new generation heteroditopic wheel based interlocked molecules in different emerging areas of science.

Development of fluorophoric [2]pseudorotaxanes and [2]rotaxane: selective sensing of Zn(II).

Fluorophoric [2]pseudorotaxanes {NiPR1(ClO4)2-NiPR3(ClO4)2} are synthesized by utilizing newly designed fluorophoric bidentate ligands (L1-L3) and a heteroditopic naphthalene containing macrocycle (NaphMC) with high yields via Ni(II) templation and π-π stacking interactions. Subsequently, a fluorophoric [2]rotaxane (NAPRTX) is established through a Cu(I) catalysed click reaction between an azide terminated pseudorotaxane, {NiPR4(ClO4)2}, which contains the newly designed fluorophoric ligand L4, and alkyne terminated bulky stopper units. All these fluorophoric [2]pseudorotaxanes and the [2]rotaxane were characterized using numerous techniques such as mass spectrometry, NMR, UV/Vis, PL, and elemental analysis, wherever applicable. Furthermore, to investigate the effect of the fluorophoric moieties, the coordinating ability of chelating units, and size and shape of the three dimensional cavity generated by the mechanical bond in the interlocked [2]rotaxane (NAPRTX), we have performed a sensing study of various metal ions. Thus, the interlocked [2]rotaxane is found to have potential as a selective fluorescent sensor for Zn(II) metal ions over other transition, alkali and alkaline earth metal ions, where the 2,2'-bipyridyl arylvinylene moiety of the axle acts as a fluorescence signalling unit.

NDI-integrated rotaxane/catenane and their interactions with anions.

Complexation of alkali and alkaline earth metal ions with the heteroditopic Phen-ester oxy-ether macrocyclic wheel (PhenMC) is established for the synthesis of interlocked molecular systems. The single crystal X-ray structure of Na-bound PhenMC confirms the hexacoordinated geometry around the Na ion in the macrocycle. Further, Ca-ion-bound PhenMC (Ca-PhenMC) is explored with a fluorophoric azide-terminated NDI (naphthalene diimide) axle (NDIAz) for the synthesis of fluorophoric [2]rotaxane (NDIROT) and [2]catenane (NDICAT) via Cu(I)-catalyzed cycloaddition reaction. Characterizations of these two new interlocked molecular systems are performed by ESI-MS, NMR, UV-vis and PL spectroscopic studies wherever applicable. Moreover, the new molecular systems are explored towards anion sensing applications via colorimetric, UV-vis-NIR, PL and other spectroscopic studies.

A Cd(ii) and Zn(ii) selective naphthyl based [2]rotaxane acts as an exclusive Zn(ii) sensor upon further functionalization with pyrene.

A new multi-functional [2]rotaxane, ROTX, has been synthesized via a Cu(i) catalysed azide-alkyne cycloaddition reaction between Ni(ii) templated azide terminated pseudorotaxane composed of a naphthalene based heteroditopic wheel, NaphMC, and an alkyne terminated stopper. Subsequently, ROTX has been functionalized with pyrene moieties to develop a bifluorophoric [2]rotaxane, PYROTX, having naphthalene and pyrene moieties. Detailed characterization of these two rotaxanes is performed by utilizing several techniques such as ESI-MS, (1D and 2D) NMR, UV/Vis and PL studies. Comparative metal ion sensing studies of NaphMC (a fluorophoric cyclic receptor), ROTX ([2]rotaxane with a naphthyl fluorophore) and PYROTX ([2]rotaxane having naphthyl and pyrene fluorophores) have been performed to determine the effect of dimensionality/functionalization on the metal ion selectivity. Although NaphMC fails to discriminate between metal ions, ROTX serves as a selective sensor for Zn(ii) and Cd(ii). Importantly, PYROTX shows exclusive selectivity towards Zn(ii) over various transition, alkali and alkaline earth metal ions including Cd(ii).

Cu(ii) templated formation of [n]pseudorotaxanes (n = 2, 3, 4) using a tris-amino ether macrocyclic wheel and multidentate axles.

A tris-amine and oxy-ether functionalised macrocyclic wheel (NaphMC) and various phenanthroline based multidentate axles (L1, L2 and L3) are utilised for the formation of [n]pseudorotaxanes (n = 2, 3, 4) in high yields via Cu(ii) temptation and π-π stacking interactions. The systematic development of threaded supramolecular architectures i.e. [2]pseudorotaxane {[2]CuPR(ClO4)2}, [3]pseudorotaxane {[3]CuPR(ClO4)4} and [4]pseudorotaxane {[4]CuPR(ClO4)6} from bidentate L1, linear tetradentate L2 and tripodal hexadentate L3 respectively is described. All the [n]pseudorotaxanes are well characterized by several spectroscopy and other experimental techniques such as electrospray ionization mass spectrometry (ESI-MS), isothermal titration calorimetric (ITC) study, UV/Vis, EPR, IR and elemental analysis. Moreover, the single crystal X-ray analysis of [2]pseudorotaxane confirmed the threading of L1 in the cavity of NaphMC, resulting in the formation of a penta-coordinated Cu(ii) ternary complex. ITC studies revealed the order of binding constant values for the formation of [n]pseudorotaxanes from the NaphMC-Cu(ii) complex and multidentate axles as L3 > L2 > L1. Finally, we have also shown the ability of Ni(ii) to act as a metal template in the formation of [n]pseudorotaxanes.

An integrated urea and halogen bond donor based receptor for superior and selective sensing of phosphates.

A new RuII based bis-heteroleptic ditopic receptor, 1[PF6]2 (C44H33F12IN10OP2Ru), having integrated anion binding iodotriazole (halogen bond donor) and urea units (-NH bond donor) is employed for selective sensing of phosphates (e.g., H2PO4- and HP2O73-). 1[PF6]2 showed superiority in phosphate sensing in CH3CN as compared to its hydrogen bond donor analogue, 2[PF6]2 (C44H34F12N10OP2Ru), non-urea halogen bond analogue, 3[PF6]2 (C38H27F12IN8P2Ru) and non-urea hydrogen bond donor analogue, 4[PF6]2 (C38H28F12N8P2Ru) in terms of enhanced binding constant values, longer excited state lifetimes and lower detection limit values. 1H-NMR, Isothermal Titration Calorimetry (ITC) and photophysical studies revealed the implementation of the combined role of both the halogen bond donor iodotriazole unit and the -NH unit of the urea moiety for selective and enhanced binding of phosphates.

A multifunctional catenated host for the efficient binding of Eu3+ and Gd3.

A new multifunctional [2]catenane is synthesized by using a phenanthroline-based heteroditopic wheel and Axle, which acts as a receptor for the efficient binding of lanthanide ions such as Eu3+ and Gd3+.

Syntheses of metallo-pseudorotaxanes, rotaxane and post-synthetically functionalized rotaxane: a comprehensive spectroscopic study and dynamic properties.

Herein, a bis-amido tris-amine macrocycle and five bipyridine-based bidentate chelating ligands were investigated towards various divalent transition metal ion (NiII, CoII, CuII, and ZnII)-templated syntheses of metallo [2]pseudorotaxanes. The formation of these ternary complexes was elucidated via different spectroscopic techniques such as ESI-MS, absorption spectroscopy, EPR spectroscopy, and single-crystal X-ray diffraction studies wherever possible. Azide-terminated NiII, CoII, CuII, ZnII-templated [2]pseudorotaxanes were explored to generate [2]rotaxane, ROT, via reaction with an alkyne-terminated triphenylene unit as a stopper under the mild reaction condition of the CuI-catalyzed azide-alkyne cycloaddition reaction. NiII-templated [2]pseudorotaxane was found to be the best precursor towards the high-yield synthesis of ROT. The interpenetrative nature of the center piece in metal-free rotaxane was also established through various spectroscopic techniques such as ESI-MS and 1D and 2D (COSY, NOESY, ROESY, and DOSY) NMR spectroscopy. Furthermore, ROT was functionalized via tri-acetylation as AcROT to incorporate three tertiary amides at the tris-amine centers; this AcROT exhibited rotamer-induced molecular motions in an interpenetrated system via the formation of multiple conformers/co-conformers. Additionally, the existence of multiple rotamers was established via variable-temperature NMR spectroscopic studies. Li+ and 12-crown-4 were found to be suitable for the reversible conformation/co-conformation fixation of tri-acetylated bis-amido tris-amine macrocyclic wheel-based rotaxane.

Polyamide-Polyamine Cryptand as Dicarboxylate Receptor: Dianion Binding Studies in the Solid State, in Solution, and in the Gas Phase.

Polyamide-polyamine hybrid macrobicycle L is explored with respect to its ability to bind α,ω-dicarboxylate anions. Potentiometric studies of protonated L with the series of dianions from succinate (suc2-) through glutarate (glu2-), α-ketoglutarate (kglu2-), adipate (adi2-), pimelate (pim2-), suberate (sub2-), to azelate (aze2-) have shown adipate preference with association constant value of K = 4900 M-1 in a H2O/DMSO (50:50 v/v) binary solvent mixture. The binding constant increases from glu2- to adi2- and then continuously decreases with the length of the anion chain. Further, potentiometric studies suggest that hydrogen bonding between the guest anions and the amide/ammonium protons of the receptor also contributes to the stability of the associations along with electrostatic interactions. Negative-mode electrospray ionization of aqueous solutions of host-guest complexes shows clear evidence for the selective formation of 1:1 complexes. Single-crystal X-ray structures of complexes of the receptor with glutaric acid, α-ketoglutaric acid, adipic acid, pimelic acid, suberic acid, and azelaic acid assist to understand the observed binding preferences. The solid-state structures reveal a size/shape complementarity between the host and the dicarboxylate anions, which is nicely reflected in the solution state binding studies.

Threading of various 'U' shaped bidentate axles into a heteroditopic macrocyclic wheel via NiII/CuII templation.

The threading of 'U' shaped bent axles having diverse functionalities (Axle1-Axle10) is investigated by using a heteroditopic amido-amine macrocyclic (MC) wheel via NiII or CuII metal ion templation. These bent shaped axles are the derivatives of 4,4'-substituted 2,2'-bipyridine, which are composed of various terminal groups like alkene, alkyne, bromide, hydroxyl and azide. Such metallo [2]pseudorotaxanes are well characterised by ESI-MS, EPR and FT-IR spectroscopic studies, UV-Vis absorption studies, elemental analysis and single-crystal X-ray diffraction studies wherever possible. Experimental evidence supports 1 : 1 : 1 ternary complexation between MC, the metal ion and axle. The single crystal X-ray structures of three CuII templated ternary complexes (PR1', PR3' and PR7') show the penta-coordination arrangement around the templating metal ion. Interestingly, judicious selection of chemical functionalities in the complementary wheel and axle components enables to show the existence of various covalent and non-covalent interactions.