Inorganic Chemistry Frontiers Best Covers of 2023

We are proud to announce the three best covers of Inorganic Chemistry Frontiers in 2023! The awarded works were chosen by our readers through a worldwide vote. To learn more about the science behind the winning pieces, read the cover articles below for free until 29 February 2024.

Uranyl-silicotungstate-containing hybrid building units {α-SiW9} and {γ-SiW10} with excellent catalytic activities in the three-component synthesis of dihydropyrimidin-2(1H)-ones

Jian-Hua Ding, Yu-Feng Liu, Zhao-Teng Tian, Pei-Jie Lin, Feng Yang, Ke Li,* Guo-Ping Yang * and Yong-Ge Wei *
Inorg. Chem. Front., 2023, 10, 3195-3201

 

From unprecedented 2,2′-bisimidazole-bridged rare earth organometallics to magnetic hysteresis in the dysprosium congener

Florian Benner and Selvan Demir *
Inorg. Chem. Front., 2023, 10, 4981-4992

XueQian Xiao, Xiao Hu, Qiming Liu, Yuling Zhang, Guo-Jun Zhang * and Shaowei Chen *
Inorg. Chem. Front., 2023, 10, 4289-4312

 

Congratulations to the winners!

We would like to express our sincere appreciation for all the support and contribution from our authors, reviewers, and readers during 2023.

Looking forward to receiving your high-quality work in 2024.

Happy New Year!

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Inorganic Chemistry Frontiers Early Career Advisory Board – Open for Nominations

We are delighted to announce the establishment of our inaugural Early Career Advisory Board at Inorganic Chemistry Frontiers. This initiative aims to provide a direct channel for engaging with early-career researchers, supporting their professional development, and infusing our journal with fresh innovative perspectives from the younger generation.

We warmly invite you to nominate emerging investigators to the board or encourage your colleagues to self-nominate before 25 February 2024.  

Role of the Early Career Advisory Board

At Inorganic Chemistry Frontiers, we value the voices of early-career researchers. Joining the board, you will be part of a dynamic group of emerging investigators, helping shape the future of a leading inorganic chemistry journal and benefiting from networking opportunities with the journal’s Editorial and Advisory Board members.

Your insights will be invaluable as you provide feedback on the journal’s scientific standards, suggest emerging topics and researchers worth featuring, and contribute to promotional and visibility initiatives within your community.

Terms of Service

Normally, members of the Early Career Advisory Board will serve a term of two years, with an option for reappointment for a maximum of two consecutive terms.

Eligibility

  • Nominations are open to researchers of any nationality from academia or industry.
  • Candidates should typically be no more than 6 years from starting an independent research position (Assistant Professor or industry equivalent); appropriate consideration will be given to those who have taken a career break, followed a different career path or work in systems where their time period to independence may vary.
  • Candidates should demonstrate a commitment to advancing inorganic chemistry through developing high-quality journals.

How to Nominate

Please email the following information to InorgChemFrontiersED@rsc.org for your nominations.

Self-nominations are very welcome. If you are interested in joining our Early Career Advisory Board, please provide:

  • An up-to-date CV which highlights your engagements in academic activities (conferences participation etc.) and services to the wider community (journals, societies, etc.)
  • Any supplementary materials, such as a brief supporting statement from an active Principal Investigator or contact information of references.

To nominate someone else, please provide:

  • Candidate’s name, position, affiliation, website URL and contact details, along with a brief description of the candidate’s research contribution and community engagement
  • Nominator’s name, position, affiliation and contact details
  • Any supporting materials, such as an up-to-date CV of the candidate

Selection Criteria

Editorial Board of the journal will consider the following aspects of all nominations as appropriate:

  • Profile within institute and/or community
  • Involvement in community and advocacy activities
  • Area and quality of research
  • Motivation to join Early Career Advisory Board

We look forward to receiving your nominations!

Kind Regards,

Prof Song Gao 
Editor-in-Chief, Inorganic Chemistry Frontiers
Sun Yat-sen University and Peking University

Dr Wenjun Liu
Executive Editor, Inorganic Chemistry Frontiers
Royal Society of Chemistry

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Bisimidazole – Exciting for Organometallics and Single-Molecule Magnets

From unprecedented 2,2′-bisimidazole-bridged rare earth organometallics to magnetic hysteresis in the dysprosium congener
Florian Benner and Selvan Demir
Inorg. Chem. Front., 2023, 10, 4981-4992
https://doi.org/10.1039/D3QI00546A

Single-molecule magnets (SMMs) are molecules that show slow magnetic relaxation, originating from a bistable magnetic ground state with a thermal barrier to spin relaxation (Ueff). Remarkably, SMM can exhibit open magnetic hysteresis loops which correspond to retaining magnetic memory just like tiny bar magnets can. This property renders SMMs exciting for potential applications in high-density information storage, magnetic refrigeration, quantum computing and spintronics. Over the last years, the SMM field exploited mononuclear dysprosium metallocenium cations as spin carriers, where the well-defined coordination sphere imposed by cyclopentadienyl ligands strongly amplifies the easy axis of the dysprosium(III) ion. To date, synthetically accessible single-ion magnets operate at best slightly above the boiling temperature of liquid nitrogen (77 K).   Consequently, it was realized that lanthanide ions must be strongly coupled to one another to increase operating temperatures, ideally towards room temperature. To this end, the nature of the bridging ligand is vital and the exploration of new organic bridging ligands along with their utility in coupling lanthanide metallocene fragments is crucial. That knowledge will aid to devise design principles of SMMs with amplified magnetic coupling between lanthanide metallocene moieties.

Recently, the group of Selvan Demir at Michigan State University implemented the bridging ligand 2,2′-bisimidazole for the first time into rare earth and magnetochemistry, where this tetranitrogen ligand connects two metallocenium units (Figure 1). The synthesized series consists of three compounds comprising the diamagnetic yttrium, the paramagnetic gadolinium (isotropic) and paramagnetic dysprosium (anisotropic) ions. Excitingly, the dinuclear dysprosium complex features SMM behavior and on the timescale of magnetic hysteresis measurements, open hysteresis loops of up to 5 K. The half-filled f-electron valence shell for trivalent gadolinium ions allows quantification of the magnetic exchange coupling since the orbital singlet affords magnetic behavior that is free of complications arising from spin-orbit coupling. Thus, dc magnetic susceptibility measurements on the respective gadolinium complex revealed weak antiferromagnetic interaction between the metal ions. Due to its comparable ionic size, the yttrium analog served as a diamagnetic surrogate to the lanthanides, enabling the in-depth investigation of the electronic structure of these complexes via spectroscopic methods and density functional theory (DFT) calculations. In this way, absorption spectra were related to the underlying electronic structure of these complexes, revealing prevalent excitations from the predominantly ligand-based frontier orbitals into metal-based higher-lying orbitals. This provided also profound insight into the redox (in)activity of the bisimidazole bridge, which, in contrast to its annulated 2,2′-bisbenzimidazole analog, showed no reactivity towards reductants or oxidants. This was primarily ascribed to the title compounds lacking accessible ligand-based low-lying π* orbitals, unlike the opposite observation for the respective bisbenzimidazole counterparts. In sum, the fact that the bisimidazole ligand retains and enhances the single-ion anisotropy of the dysprosium ions while providing a wealth of substitution sites for future chemical modification renders this ligand system highly promising for the construction of higher nuclearity systems.

Figure 1. A: Schematic view of the bisimidazole-bridged rare earth metallocene complexes. B: Structure of the complexes as determined through single-crystal X-ray diffraction analysis. C: Plot of the bisimidazole-centered highest occupied molecular orbital of the yttrium complex.

 

Figure 2. A: Absorption spectra of the rare earth complexes in the ultraviolet/visible region of the electromagnetic spectrum. B: Dynamic magnetic measurement revealed slow magnetic relaxation and single-molecule magnet behavior for the dysprosium complex.

Corresponding Author:

Selvan Demir is an Assistant Professor of Chemistry at Michigan State University. She received a Dr. rer. nat. in Chemistry from the University of Cologne researching on scandium solid state chemistry with Prof. Gerd Meyer and scandium organometallic chemistry with Prof. William J. Evans at the University of California, Irvine. Subsequently, she was a Postdoctoral Scholar, where she conducted research on lanthanide-based single-molecule magnets and porous aromatic frameworks with Prof. Jeffrey R. Long at the University of California, Berkeley. Simultaneously, she explored the transuranics with Dr. David K. Shuh at the Lawrence Berkeley National Laboratory. Afterwards, she took up a junior professorship of inorganic chemistry at the University of Göttingen. Since 2019, she researches with her group at Michigan State University, on various areas surrounding the chemistry of the rare earth elements and actinides. Her research program has a strong emphasis on organometallic chemistry, small molecule activation, organic radicals, single-molecule magnets, qubits, bismuth chemistry, dibenzocyclooctatetraene chemistry, and lanthanide/actinide separations.

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Efficient Fluorescence of Alkali Metal Carbazolides

In recent years, derivatives of carbazole have been studied intensively with focus on their optical properties to scry for applicability as materials in OLEDs and OFETs. Fine tuning of the electronic properties of the materials was achieved by a large variety of substitution patterns both on the central nitrogen atom and the carbon periphery.

Recently, the group of Dr. Hinz (Karlsruhe Institute of Technology, Germany) has investigated a series of alkali metal carbazolides with bulky arenes in positions 1 and 8 of the carbazole scaffold (see Figure 1). The alkali metal complexes of the type [(Cbz)M] show visible fluorescence with emissions maxima in the range of 520 and 460 nm in dependence of the metal ion. Quantum yields of up to 29% in the solid state were measured for the rubidium derivative.

The electronic transitions were rationalised with the aid of TD-DFT calculations. Upon HOMO→LUMO+1 excitation, density shifts from the carbazole scaffold to the arenes in positions 1 and 8 and thus are intraligand transitions. The geometry of the complexes only change slightly upon excitation which enables the highly efficient fluorescence.

Coordination of additional toluene molecules to the alkali metal shifts the emission maximum to lower energy and enables a second emission band arising from an interligand excitation from the carbazole to a toluene molecule. The quantum yields for the complexes in toluene solution are even higher than in the solid state and reach 100% for the lithium complex.

Figure 1 Preparation of the rubidium carbazolide complex, its molecular structure, luminescence behaviour and the orbitals involved in the excitation and emission process.

Corresponding author:

Alexander Hinz studied chemistry in Rostock, Germany, and is currently a junior group leader at the Karlsruhe Institute of Technology. The work of the Hinz group is focused on molecular main group chemistry and devoted to the investigation of low-coordinated, but highly reactive compounds.

E-mail: alexander.hinz@kit.edu

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Emerging Investigator: Jian Lin at Xi’an Jiaotong University, China

Emerging Investigator: Jian Lin

Position           Professor

Postdoc          2014–2016   Argonne National Laboratory

Education       2010–2014   University of Notre Dame (USA)           Ph.D.

                       20062009   China Agricultural University                 M.Sc.

                       20022006   China Agricultural University                 B.Sc. 

Website           https://gr.xjtu.edu.cn/en/web/jianlin/home

ORCID            0000-0002-3536-220X            Google Scholar

Read Jian Lin’s Emerging Investigator Series article in Inorganic Chemistry Frontiers and learn more about him.

     
  Topological control of metal–organic frameworks toward highly sensitive and selective detection of chromate and dichromate  
Zi-Jian Li, Yu Ju, Xiao-Ling Wu, Xiaoyun Li, Jie Qiu, Yongxin Li, Zhi-Hui Zhang, Ming-Yang He, Linjuan Zhang, Jian-Qiang Wang and Jian Lin*

 

A synthetic modulation approach has given rise to two topologically distinct thorium-based MOFs, whose polymorphism allows for elucidating how the structure of MOF, in isolation, influences the sensing efficacy of Cr(VI) oxyanions.

 

  From the themed collection: Frontiers Emerging Investigator Series  
  The article was first published on 04 Jan 2023  
  Inorg. Chem. Front., 2023, 10, 1721-1730  
  https://doi.org/10.1039/D2QI02631G  
     

My research interests

Key words: actinide, inorganic chemistry, coordination chemistry, radiochemistry, nuclear science
My research interests mainly focus on developing new synthetic strategies to access crystalline materials, including metal–organic frameworks and clusters, for potential applications in ionizing radiation detection, radionuclide separation, and chemosensing.

10 Facts about me

I published my first academic article in Inorganic Chemistry when I was a graduate student in Prof. Thomas Albrecht-Schoenzart’s group.

An accomplishment I’m particularly proud of is our work of thorium-based nanoclusters, which show photochromism, fluorochromism, and piezochromism.

I am most passionate about my work in actinide chemistry because actinides are the most fascinating elements in the periodic table.

I advise my students to work smart, not just hard.

One of my hidden talents is making crystals.

If I were not a chemist, I would probably be a photographer.

My favourite sport is basketball and Yao Ming is my favourite basketball player.

One thing I cannot live without is my daughter, who has a beautiful and infectious laugh.

My passion besides work is travel and my best travel experience was in New Zealand.

My favourite inspirational quote: “It’s not who you are underneath but what you do that defines you.”

Click to find out our Emerging Investigators and their work

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New members of radical bridged Ln2 metallocene single-molecule magnets based on the unsubstituted 1,2,4,5-tetrazine ligand

Single-molecule magnets (SMMs) are molecules that retain the slow relaxation of their magnetization upon removal of an applied magnetic field, acting as magnets below a characteristic temperature known as the blocking temperature. Research in this field has recently focused on the use of radicals as ligands to enhance the performance of SMMs through the exchange coupling of the radical- and metal-based spins. The strong interaction between the spin of the radical with the unpaired electrons of a metal ion effectively suppresses the quantum tunneling of the magnetization (QTM) and fast spin relaxation pathways involving spin excited states, thus promoting a thermal relaxation pathway for magnetization reversal. The latter is particularly important when designing lanthanide (Ln) based SMMs as the core-like nature of the 4f orbitals makes magnetic coupling challenging and thus they tend to suffer from through-barrier relaxation of the magnetization (i.e., QTM, Raman and direct mechanisms).

To this day several attempts towards this direction have been made leading to the isolation of strongly coupled Ln SMMs with the N2•3--based family exhibiting very good magnetic performance. However, the rational incorporation of the N2 species into complexes is a synthetic challenge and it does not offer any room for structural modification. For this reason, other radicals, such as tetrazines have been explored by the group of Prof. Muralee Murugesu of the University of Ottawa. In the past the researchers had successfully incorporated the 1,2,4,5-tetrazine radical anion (tz•−) into tetranuclear “Ln4” metallocenes which led to strong magnetic coupling and significant magnetic hysteresis (Hc = 3 T).

Recently, the researchers aimed to isolate a dinuclear building block so that the role of the bridging ligand in the overall magnetic coupling in Ln systems can be better understood. In further detail, they have utilized the high performing {Cp*2LnIII}+ moieties and bridge them by employing the tz•−, leading to the isolation of a new family of radical-bridged Ln metallocenes: [(Cp*2LnIII)2(tz•−)(THF)2](BPh4), (Ln = Gd (1), Tb (2), Dy (3); THF = tetrahydrofuran).

Figure 1. A) Synthesis of the radical-bridged dinuclear compounds (1-3). (B) Molecular structure of 3. Partial labelling and omission of the BPh4- moiety and H-atoms have been employed for clarity. The solid teal lines represent the orientation of the principal magnetic axes of the ground Kramers doublet. C) Variable temperature dc susceptibility of 1 (teal circles), 2 (blue circles) and 3 (magenta circles) under an applied field of 1000 Oe. The solid red line represents the fit as determined from the application of the -2J formalism. Insert: Simplified illustration of the two J-model which was used to fit the data highlighting the antiparallel spin alignment of the LnIII ions with respect to the tz•- ligand.

They showed that a strong magnetic coupling between the LnIII ions and the tz•− was achieved, revealing a JGd-rad = -7.2 cm-1 for 1 which is even comparable to some N2•3- bridged SMMs. Due to this, both 2 and 3 displayed zero-field SMM behavior with slow relaxation of the magnetization and magnetic hysteresis.

Figure 2 Left: Frequency-dependence of the out-of-phase magnetic susceptibility (χ’’) at zero-field for 2 (A) and 3 (D) at the respective temperature regions. Solid lines represent fits to the generalized Debye model. Middle: Cole-Cole plots for 2 (B) and 3 (E) at the respective temperature regions (Hdc = 0 Oe). Solid lines represent fits to the generalized Debye model. Right: Temperature-dependence of the relaxation times (τ) for 2 (C) and 3 (F) with the respective estimated standard deviations (gray bars). The estimated standard deviations of the τ were calculated from the α-parameters of the generalized Debye fits and the log-normal distribution. The solid red lines represent the best-fit while the dashed orange and purple lines in (C) represent the individual components of the magnetic relaxation for QTM and Orbach processes, respectively.

Ab initio calculations verified the strong antiferromagnetic Ln-rad coupling and showed that the magnetic state of 2 and 3 can be interpreted as a “giant-spin” where the relaxation of the magnetization is related to changes in the magnetic state of the overall exchange-coupled system. The slow relaxation of these SMMs is mediated via thermally activated processes through the first excited KDs which correspond to an Ising-type ferrimagnetic spin configuration where the magnetic moments of the LnIII ions are co-aligned while the magnetic moment of the radical points to the opposite direction.

The researchers believe that the results presented in this work will be helpful for future strategies on designing new lanthanide metal complexes employing radical ligands in the pursuit of new strongly-coupled zero field SMMs.

Corresponding author:

Prof. Muralee Murugesu
University of Ottawa

Prof. Muralee Murugesu received his PhD from the University of Karlsruhe in 2002 under the supervision of Prof. A. K. Powell. He undertook postdoctoral stays at the University of Florida (2003–2005) with Prof. G. Christou, and jointly at the University of California, Berkeley and the University of California, San Francisco under the supervision of Prof. J. R. Long and the Nobel Laureate Prof. S. Pruissner (2005–2006). In 2006, he joined the University of Ottawa as an assistant professor and since 2015 he is a full professor. Prof. Murugesu’s research focuses on the design and development of Single-Molecule Magnets, Metal-Organic Frameworks and High-Energy materials.

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Inorganic Chemistry Frontiers Best Covers of 2022

We are proud to announce the three best covers of Inorganic Chemistry Frontiers in 2022! The awarded work was chosen by our readers through a worldwide vote. To learn more about the science behind the winning pieces, read the cover articles below.

Self-templating synthesis of heteroatom-doped large-scalable carbon anodes for high-performance lithium-ion batteries

Ghulam Yasin,* Muhammad Arif, Jiameng Ma, Shumaila Ibraheem, Donglin Yu, Lipeng Zhang, Dong Liu* and Liming Dai*
Inorg. Chem. Front., 2022, 9, 1058-1069

 

Ligand-regulated metal–organic frameworks for synergistic photoredox and nickel catalysis

Yang Tang, Liang Zhao,* Guanfeng Ji, Yu Zhang, Cheng He, Yefei Wang, Jianwei Wei and Chunying Duan
Inorg. Chem. Front., 2022, 9, 3116-3129

Xiaoxiao Niu, Meixiang Wang, Mengyu Zhang, Rui Cao, Zhaodi Liu,* Fuying Hao, Liangquan Sheng and Huajie Xu*
Inorg. Chem. Front., 2022, 9, 4582-4593

 

Congratulations to the winners!

We would like to express our sincere appreciation for all the support and contribution from our authors, reviewers, and readers during 2022.

Looking forward to receiving your high-quality work in 2023.

Happy Lunar New Year!

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Emerging Investigator: Justin J. Wilson from Cornell University, USA

Emerging Investigator: Justin J. Wilson

Position           Associate Professor

Postdoc          2013–2015  Los Alamos National Laboratory

Education       2008–2013  Massachusetts Institute of Technology   Ph.D.

                       20042008  UC Berkeley                                            B.Sc.

Website           https://wilson.chem.cornell.edu/

ORCID            0000-0002-4086-7982            Google Scholar

Read Justin J. Wilson’s Emerging Investigator Series article in Inorganic Chemistry Frontiers and learn more about him.

     
  A ferrocene-containing analogue of the MCU inhibitor Ru265 with increased cell permeability  
Zhouyang Huang, Jesse A. Spivey, Samantha N. MacMillan and Justin J. Wilson*

 

An analogue of the mitochondrial calcium uniporter (MCU) inhibitor Ru265 containing axial ferrocenecarboxylate ligands is reported. This new complex exhibits enhanced cellular uptake compared to the parent compound Ru265.

 

  From the themed collection: Frontiers Emerging Investigator Series  
  The article was first published on 06 Dec 2022  
  Inorg. Chem. Front., 2023, Advance Article  
  https://doi.org/10.1039/D2QI02183H  
     

My research interests

Key words: medicinal inorganic chemistry, bioinorganic chemistry, f-element coordination chemistry, radiopharmaceutical chemistry
My research interests broadly span the field of metals in medicine and f-element coordination chemistry. Our group is interested in designing coordination complexes so that they have properties that are suitable for different biomedical applications, including both therapy and diagnosis. Within this area, we have developed metal-based mitochondrial calcium uptake inhibitors that show cytoprotective effects against in vitro models of ischemic stroke. Furthermore, we have interests in the realm of nuclear medicine. In this area, our group design chelating agents that can be used to deliver different diagnostic and therapeutic radiometals to diseased sites in patients. In the general realm of f-element coordination chemistry, we are working to apply our chelators for different applications, including rare earth element separation and isolation.

10 Facts about me

I published my first academic article as a graduate student in Prof. Steve Lippard’s lab. As a young graduate student, it was exciting to translate results from the lab into a tangible product (manuscript), but it also made me realize that there was a lot that goes into every manuscript that is published besides just the research!

An accomplishment I’m particularly proud of is our work in actinium-225 chelation chemistry. Thus far, this work seems like it may have some immediate near-future applications that can harness the therapeutic properties of this radionuclide.

I am most passionate about my work in mentoring students and postdocs because they are dynamic products. Instead of a manuscript or interesting scientific result, mentees go on to do amazing things that I never would have envisioned.

My favourite morning routine is swimming. Starting the day with a good swim gets my head clear for work.

One of my hidden talents is playing guitar. As an undergraduate, I used to play with a lot of my friends.

One thing I cannot live without is my family. Seeing them at the end of everyday always puts work and its demands into perspective.

I advise my students to be curious about everything. If a result doesn’t turn out the way you expect it to, think about if that result could mean something potentially even more impactful.

The most important quality of a mentor is to let students come up with their own ideas and pursue them, but with guidance.

My passion besides work is food and travel. It’s always exciting to try and see new things.

A recent epiphany: you can say “no” to requests on your time. It’s always exciting to participate in different projects, reviewing assignments, and committees, but at a certain point you need to recognize what you can manage effectively.

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Emerging Investigator: Hongwei Yu from Tianjin University of Technology, China

Emerging Investigator: Hongwei Yu

Position             Professor

Postdoc             2016–2017   Northwestern University (USA)

        2014–2016   University of Houston (USA)

Education          2009–2014   Xinjiang Technical Institute of                                                                       Physics &Chemistry, CAS        Ph.D.

                          2005–2009  Jilin University (China)              B.Eng.

ORCID               0000-0002-5607-0628

Read Hongwei Yu’s Emerging Investigator Series article on Inorganic Chemistry Frontiers and learn more about him.

     
  The exploration of new infrared nonlinear optical crystals based on the polymorphism of BaGa4S7  
Zhen Qian, Haonan Liu, Yujie Zhang, Hongping Wu, Zhanggui Hu, Jiyang Wang, Yicheng Wu and Hongwei Yu*

 

Two new polymorphism of BaGa4S7 was successfully discovered and synthesized. Among them, β-BaGa4S7 exhibits the best balance among a large phase-matching SHG response and a wide band gap, as well as the stable physicochemical property.

 

  From the themed collection: Frontiers Emerging Investigator Series  
  The article was first published on 26 Jul 2022  
  Inorg. Chem. Front., 2022, Advance Article  
  https://doi.org/10.1039/D2QI01263D  
     

My research interests

Key words: nonlinear optical crystals, solid state chemistry, crystal growth
Nonlinear optical (NLO) crystals—the unique materials capable of generating coherent radiation at various difficult-to-access wavelengths through frequency conversion technologies—are of particular importance for laser and photonic technologies. Currently, the commercial NLO crystals are mainly used in the ultraviolet (UV) and visible regions. However, in the deep-UV (λ < 200 nm) and mid-IR (3 μm < λ < 20 μm) regions, the available NLO crystals are still limited. Therefore, my research interests are to design, synthesize and grow new NLO crystals for the laser output in deep-UV and IR regions. The materials classes I am interested in include borates, phosphates, chalcogenides and some heteroanionic compounds, etc.

10 Facts about me

I published my first academic article on synthesis, structure and characterization of a new tripotassium cadmium pentaborate in Journal of Solid State Chemistry in 2011.

An accomplishment I’m particularly proud of is that I have synthesized hundreds of new inorganic crystals and determined their structures by single-crystal X-ray diffraction.

My favourite sport is mountain-climbing.  

One of my hidden talents is singing.

One thing I cannot live without is delicious food.

My favorite books were tales of mystery when I was a child.

I always believe that a good chemist would also be a good cooker.

In five years, I hope to get an excellent NLO material for achieving highly effective output of deep-UV lasers.

I chose chemistry as a career because chemistry is magical; it can create a new material world.

The best advice I have ever been given is to cherish everything around you.

Click to find out our Emerging Investigators and their work

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Dynamic lanthanide exchange between quadruple-stranded cages: the effect of ionic radius differences on kinetics and thermodynamics

Advances in the coordination chemistry of multinuclear compounds have been exploited to drive the self-assembly of many new discrete metallo-supramolecular motifs. Due to the nature of the metal-ligand interactions, many of these systems have a dynamic character with reversible association and dissociation able to generate complex mixtures. Unveil such dynamic behaviours, it is a priority to fully understand, control and design their functional properties. Among metallo-supramolecular systems, lanthanide (Ln) based architectures attracts much attention due to their remarkable optical and magnetic properties. However, design and control of the final supramolecule is very challenging due to the inner nature of the 4f orbitals and consequent small ligand-field effects. There is, however, a steady variation of the effective ionic radius (EIR) across the series, the so called “lanthanide contraction”. Although the radii difference (ΔEIR) is quite small (ca. 0.20 Å between La3+ and Lu3+ and ca. 0.02 Å between two consecutive lanthanides), it can have important chemical consequences on the nature and features of supramolecular complexes.

Recently, a group headed by Marzio Rancan of ICMATE-CNR (Italy) and collaborators from the University of Padova (Italy) and Dortmund University (Germany) have demonstrated that ΔEIR strongly affects the kinetics of Ln ions exchange between preassembled quadruple-stranded [Ln2L4]2 cages (Figure 1).

Figure 1. (a) Self-assembly of seven [Ln2L4]2− cages (Ln = La, Nd, Eu, Tb, Er, Tm and Lu). (b) Dynamic Ln3+ ion exchange equilibrium between two pre-assembled cages and (c) exponential trend of the kinetic constants depending on the Ln ΔEIR.

The process has been qualitatively and quantitatively characterized by time-dependent electrospray ionization mass spectrometry (ESI-MS). Mixing a series of two homonuclear [LnA2L4]2− and [LnB2L4]2− with increasing Ln3+ ΔEIR always leads to the formation of a statistical mixture of homo- and heteronuclear helicates due to the Ln exchange. All the studied systems have an equilibrium constant close to K = 4. The Ln3+ ΔEIR, hence, does not affect the thermodynamics of the process that is mainly governed by statistical factors and entropy-driven. On the other hand, they demonstrate that the rate of the dynamic ion exchange is Ln radius-dependent (Figure 1b). The kinetic constants of the forward and backward reactions revealed an exponential trend depending on the Ln3+ ΔEIR of the two homonuclear pre-assembled cages (Figure 1c): from the minimum to the maximum value of ΔEIR, the kinetic constants increase by three orders of magnitude. This fundamental study hints new tools and guidelines to study dynamic processes in metallo-supramolecular ensembles, and for the precise preparation and control of lanthanide-based mixed coordination-driven systems.

Corresponding author:

Marzio Rancan is a Research Fellow at ICMATE-CNR (Italy). He received his PhD in Molecular Sciences at the University of Padova in 2009. He did post-doctoral studies at CNR, University of Padova and spent one year in the Molecular Magnetism Group at The University of Manchester (UK).  His current research is focused on the synthesis and characterization of coordination-driven molecular and supramolecular architectures with functional properties. He is the author of about 60 articles.

WEBSITE: http://wwwdisc.chimica.unipd.it/FMNLab/index.html

ORCID: https://orcid.org/0000-0001-9967-5283

RESEARCHGATE: https://www.researchgate.net/profile/Marzio-Rancan

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