News

New Publication in Inorganic Chemistry:

Many congratulations to Dawn E. Barry, who in collaboration with Komala Pandurangan, Aramballi Jayant Savyasachi, Robert D. Peacock (University of Glasgow) and Jonathan A. Kitchen (Massey University) and their contribution: “Formation of enantiomerically pure luminescent triple-stranded dimetallic europium helicates and their corresponding hierarchical self-assembly formation in protic polar solutions” accepted for publication in Inorg. Chem. (DOI:10.1021/acs.inorgchem.0c00058). The work was supported by Science Foundation Ireland (SFI) and demonstrates the use of lanthanide directed synthesis of supramolecular structures from chiral organic ligands, and their application in the formation of higher order (hierarchical) structures (microparticles) which were analysed using  high-resolution imaging facilities here at the AML unit (part of AMBER and CRANN).

 

  1. Many congratulations to Jason on his paper “Aggregation induced emission (AIE) active 4-amino-1,8-naphthalimide-Tröger’s base for the selective sensing of chemical explosives in competitive aqueous media”, which has been accepted in Chem. Commun., (DOI: 10.1039/c9cc08457f). The synthesis of the target ligand (shown below) and all the sensing/supramolecular/materials aspects of the work was carried out by Jason in collaboration with Prof. Sankarasekaran Shanmugaraju (Raju) from the Indian Institute of Technology Palakkad, Kerala (https://iitpkd.ac.in/people/shanmugam) and Oxana (form the TG research group), while the computational part of the work was overseen and executed by Deivasigamani Umadevi in collaboration with Prof. Graeme W. Watson from the School of Chemistry. This work, once again, demonstrates the versatility of the naphthalimide-Tröger’s base building unit within supramolecular chemistry.

Website photo 2 07-02-2020

Anna’s Paper featured JOC webpage

It is an incredible time of the year for Doctor Anna Aletti! After her graduation ceremony, in fact, we are delighted to report another great news about her. Anna’s paper, published on the Journal of Organic Chemistry  (J. Org. Chem., 2019, 84 (7), pp 4221–4228; DOI:10.1021/acs.joc.9b00219) was featured on their webpage. The work, entitled “Halide-Controlled Extending–Shrinking Motion of a Covalent Cage” was a collaborative project that was headed up by Anna’s former mentor at Department of Chemistry, University of Pavia, Professor Valeria Amendola and was part of Anna’s PhD thesis here in TCD.

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Way to go Anna, once again, congratulations!

New work on 2-picolyl derived naphthalene diimide and bis-phthalimide ligands accepted

Many congratulations to June, now in her second PhD year, who has had her paper with Chris Hawes (former member of the TG Group and now and independent lecturer at the School of Chemical and Physical Sciences, Keele University, UK, named “Crystallographic studies of 2-picolyl substituted naphthalene diimide and bis-phthalimide ligands and their supramolecular coordination chemistry”, accepted for publication in CrystEngComm (DOI: 10.1039/C8CE01756E). This work is another excellent outcome of a very fruitful collaboration between the group and Chris, based on exploring the supramolecular application of naphthalene-based building blocks with various d-metal ions, featuring extended analysis of the various complexes formed by using single crystal structure analysis, but Chris was instrumental (as well as Brendan Twamley) in training several members of the TG group in carrying out their own X-ray analysis.Cryst

Good job!

New work on the luminescent sensing of organic solvents accepted

Many congratulations to Sachi, Bruno and David, who have had their paper on the generation of highly luminescent functional solid-state material, “Self-assembled bright luminescent hierarchical materials from a tripodal benzoate antenna and heptadentate Eu(III) and Tb(III) cyclen complexes” accepted in Frontiers of Chemical Science and Engineering (Front. Chem. Sci. Eng. 2019, DOI:10.1007/s11705-018-1762-3). This work, achieved in collaboration with the Prof. Wolfgang Schmitt research group here at TCD covers the use of self-assembly between cyclen-based lanthanide (Europium and Terbium) complexes and a tripodal ligand which yields a luminescent amorphous material (red and green respectively, as shown below) that can be used for the sensing of solvents such as MeOH, CH3CN and THF.

Sachi + Bruno

New Dalton Frontier Article on lanthanide luminescent soft-material published

Many congratulations to Oxana, Sam and Sachi, who had their invited Frontier article accepted in Dalton Transaction, “Recent advances in the development of luminescent lanthanide-based supramolecular polymers and soft materials” (Dalton Trans., 2018, 47, 16377-16387. DOI:10.1039/C8DT03768J). This work reviews some of the most recent use of luminescent lanthanides ions as crosslinking moieties to generate functional soft materials, giving the readership of Dalton a fantastic inside into this fast-growing area of material research.

Oxana, Sam Sachi

New paper accepted in Dalton Transactions!

Many congratulations to Trinity College Dublin team Dr. Oxana Kotova, Dr. Steve Comby, Dr. Komala Pandurangan (now at Jawaharlal Nehru Centre for Advanced Scientific Research (JNCASR)), Dr. Floriana Stomeo (now at IPSEN Pharma), Dr. John E. O’Brien and Dr. Martin Feeney who in collaboration with Dr. Robert D. Peacock from University of Glasgow and Prof. Colin P. McCoy from Queen’s University Belfast who have had their paper entitled “The effect of the linker size in C2-symmetrical chiral ligands on the self-assembly formation of luminescent triple-stranded di-metallic Eu(III) helicates in solution” accepted in Dalton Transactions.

The article discussed the formation of chiral, luminescent [Eu2:L3] assemblies with high stability constants in solution. However, it was found that the composition of the assemblies in the solid state was more complex. The chirality of the studied systems allowed us to investigate their formation using various techniques including circular dichroism and circularly polarised luminescence spectroscopies and help their development towards materials for the applications in electronics for virtual reality applications (3D screens) and in medical diagnostic.

Graphical Abstract

The article is available online at:  https://pubs.rsc.org/en/content/articlelanding/2018/dt/c8dt02753f#!divAbstract

New paper accepted in Chem. Commun.

Many congratulations to Dr. Sankarasekaran Shanmugaraju (Raju), Dr. Bjørn la Cour Poulsen (former PhD student), Dr. Aramballi J. Savyasachi, Hannah L. Dalton and Dr. Chris Hawes (now at Keele University, UK) who have in collaboration with Prof. Graeme Watson and Dr. D. Umadevi (School of Chemistry, TCD) have had their paper entitled: “Synthesis, structural characterisation and antiproliferative activity of a new fluorescent 4-amino-1,8-naphthalimide Tröger’s base-Ru(II)-curcumin organometallic conjugate” accepted for publication in Chem. Commun.

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In this communication, they have reported the synthesis, photophysics and biological investigation of fluorescent 4‐amino‐1,8‐naphthalimide Tröger’s bases and a new Tröger’s base p‐cymene‐Ru(II)‐curcumin organometallic  conjugate;  these  compounds  showed  fast  cellular  uptake  and  displayed  good  luminescence  and  cytotoxic against cervical cancer cells.

The journal Chem. Commun. is published by the RSC and the paper is now available online for early view: 10.1039/C8CC01584H

Chem. Soc. Review on Ru(II) polypyridyl complexes

Congratulations to group alumnus, and continuing coworker, Fergus Poynton (now a PD researcher in the School of Medicine, TCD) on their bumper review (over 50 pages in print, 465 references) available now online at Chemical Society Reviews! The review appears in a themed collection on Imaging Agents and was co-written with previous TG group members Dr. Sandra Bright (now HRPA), Dr, Salvador Blasco (now an Associated Professor at CEU Cardenal Herrera University) along with Profs. John M. Kelly and D. Clive Williams (TCD).

The review covers extensively the development of Ru(II) polypyridyl complexes for both in vitro cellular imaging and in vivo therapeutic application, highlighting the diversity and potential of these systems in a variety of complexes. The article charts the developments and exploration of photophysical properties, structural variations and biological studies over recent years and ends with an apt discussion of the concerns and importance of reproducibilty in academic clinical and drug development studies.

Well done to all, this is sure to become an important source as the field moves forwards! Read it now at RSC Publishing.

3 New Articles from Raju published in RSC Journals

Congratulation Dr. Sankarasekaran Shanmugaraju (Raju) on a hat-trick of publication recently out in Organic & Biomolecular Chemistry, Chem. Commun and Journal of Material Chemistry A.

In Organic & Biomolecular Chemistry, working with Chris and Sachi as well as group alumni Jon Kitchen and Salvador Blasco, he reported a novel one-pot synthetic strategy for the synthesis of a family of N-alkyl-1,8-naphthalimide based Tröger’s bases via a nucleophilic substitution reaction of a common ‘precursor’ N-aryl-1,8-naphthalimide Tröger’s base and aliphatic primary amine, neat at 80 °C.

In Chem. Commun the synthesis and structural characterization of two novel supramolecular coordination polymers TB-Co-CP and TB-Cd-CP was described, containing Tröger’s base structural motifs, from a novel V-shaped 4-amino-1,8-naphthalimide derived Tröger’s base luminescent scaffold. These are the second examples of such systems, and the first to be structurally characterised through X-ray diffraction analysis, which demonstrated that, in each case, substantial face-to-face π-π interactions prevail the extended structures, leading to 1D-supramolecular polymeric networks. These results are of major importance in demonstrating the application of NapTB in coordination and inorganic supramolecular chemistry. This communication was published in a special issue on “chemosensor and molecular logic”. Also, the work was featured as an inside front cover!    

The very recent article published in Journal of Material Chemistry A, Raju reported a Tröger’s base-functionalised covalent organic polymer (TB-COP) which was used as an adsorbent/molecular filter for the efficient removal of secondary chemical explosives picric acid (PA) from water. The extraction of PA was also clearly visible to the naked eye, where the yellow colored PA solution became transparent upon addition of TB-COP. Importantly, TB-COP could be used to store PA over a long period of time in a safe manner, without any leakage or any significant loss in extraction efficiency. Moreover, the polymer could be reused for several adsorption cycles, as PA could be released back into solution by simply changing the pH of the aqueous media. This makes TB-COP an extremely promising material for the selective and efficient removal of picric acid from water, as well as TB-COP can be considered as being a ‘fast’ and naked eye colorimetric indicator for such analytes.

 

Congrats to Raju and collaborators for these excellent articles!

Sachi’s review on supramolecular polymers and functional soft materials available in Chem

Congratulations to Sachi on the publication of his review “Supramolecular Chemistry: A Toolkit for Soft Functional Materials and Organic Particles” now available online in the journal Chem. The review discusses the application of supramolecular chemistry towards the development of soft materials and exploring their application. The article discusses the progress from the past 10 years of exciting research in the field. He highlights how the supramolecular approach has emerged as a toolkit with remarkable capability for the assembly of rationally designed building blocks, which precisely organize in three-dimensional space to form intricate molecular assemblies as well as bulk material with functional properties. This potential in supramolecular chemistry has emerged as a platform for the discovery of new systems and/or novel applications for existing ones, particularly in soft functional materials.

Have a read of Sachi’s review for free, courtesy of the Publishers Cell Press and Elsevier, until the 29th December 2017 at https://authors.elsevier.com/a/1W1D~8jWHDxiaP.

Well done Sachi and co-workers on your achievement!