65th DIC Anniversary Symposium at San Diego ACS National Meeting

Morning Session Alison Butler, presiding

The Division of Inorganic Chemistry

Andy Borovik (UC Irvine), DIC Chair 2022,

Introduction

Harry B. Gray (Caltech)

“Celebrating 65 Years of Inorganic Chemistry”

In the fall of 1957, the American Chemical Society approved the formation of a Division of Inorganic Chemistry. The inorganic group at Northwestern, which I had just joined, celebrated our release from governance by the Division of Physical Chemistry. Here we are, 65 years later, doing groundbreaking work in coordination chemistry, organometallic chemistry, bioinorganic chemistry, solid state chemistry, nanoscience, and sustainable energy and environment, all relevant to the grand challenges in 21^st century science and technology. I invite you to take a tour down memory lane with me.

Organometallics Subdivision [since 1967]

Marcetta Darensbourg (Texas A&M), 1983 Subdivision Chair

“A Forest Gump-ian Journey in Organometallic Chemistry (1970 – now)”

A random walk (run?) through the “Halpern Files” to the influential Pingree Park Organometallic Symposium headed by Bergman, Bercaw and Grubbs—amongst others. A “Remember Chicago”, completely oversubscribed workshop in how to handle our fragile, electron-loaded organometallics, epitomized in the Ellis, ever lower valent, “treacherous” metal carbonyl anions. An early sojourn to the Muetterties labs for introduction to the entire periodic table and onward to the mecca of triple decker sandwiches in the Klaus Jonas Labs at the MPI Muelheim. The epiphany provided by the Parshall “Homogeneous Catalysis” book and the ultimate sighting of organometallic bioelectrocatalysts in biology—these are the personal sources for this short lecture.

Alison Fout (UIUC), 2022 Subdivision Chair

“Reactivity of “CCC” iron and cobalt pincer complexes with parahydrogen”

Developing catalysts capable of reacting with parahydrogen is challenging. For parahydrogen induced polarization to occur, closed-shell catalysts are preferred. A bis(carbene) pincer complex bound to either iron or cobalt afforded diamagnetic complexes that react with parahydrogen. Specifically, the (CCC)Co catalyst has shown to hyperpolarize a variety of olefinic substrates including isoprene via a non-hydrogenative PHIP-IE mechanism. Mechanistic studies, reactivity, and modifications to the pincer ligands will be discussed.

Solid State Subdivision [since 1983]

Galen Stucky (UC Santa Barbara), 1983 Subdivision Chair

“Solid state chemistry: Infinite compositions, properties, and applicability”

Solid state chemistry has been driven by the dream of attaining apparently unreachable goals, and doing it by identifying, for example, how to make use of parts per million or less non-stoichiometric defect chemistry; the high-resolution integration of transition states and diffusion kinetics; non-equilibrium phase transformations; and, coupling the concepts of atomic-scale quantum states with macroscale physical properties. The impact of the evolution of the resulting science and technology over the past 50 years has been of the highest magnitude, as evidenced by commercial global applications such as the transition of the early transistors to the current nanoscale computer chips; the conversion of high-cost incandescent lighting and displays to energy-efficient LED technology; the development of high-turnover, efficient catalysts for high-volume chemical transformations; energy storage and conversion capabilities that are predicted in California to give us an all-electrical transportation system by 2050; and, the tools needed to monitor and to hopefully mediate ongoing global climate change. This has been done, as promoted by the Materials Genome Initiative, by the creation of large database approaches utilizing high throughput and artificial intelligence to facilitate the transition from concept to application. The solid state chemists of the American Chemical Society have been, and are, an important part of this revolution in science and technology.\

Boniface Fokwa (UC Riverside), 2022 Subdivision Chair

“Earth-abundant boride electrocatalysts for hydrogen production: Importance of 1D and 2D boron units”

The electrolysis of water is considered as a clean mean for large scale hydrogen gas production. However, this large-scale production is still hindered by the high cost and scarcity of noble metal catalysts such as Pt. Recently, non-noble metal materials have emerged as highly active electrocatalysts (AlB₂-type) for the hydrogen evolution reaction (HER) to produce hydrogen. Our recent research found that α- MoB₂ exhibits high HER activity. In addition, density functional theory (DFT) calculations show that several surfaces of AlB₂-type MoB₂ (α-MoB₂) are active and the optimum evolution of H₂ occurs on the graphene-like B-terminated {001} surface. Furthermore, DFT and experiments demonstrate that α-MoB₂ is more HER active than β-MoB₂, due to the presence of 50% more graphene-like boron layers in the former. It was recently also found that FeB B₂ is highly active for overall water splitting in basic solution. To examine the distinct activities of metal diboride as HER electrocatalysts and demonstrate how different transition metals could affect the graphene-like boron layer, DFT was applied to investigate the H-surface adsorption process on MB₂ (M = Ti, Zr, Hf, V, Nb, Ta, Cr, Mo, W). Our results indicate that the H-surface binding energy decreases as the electronegativity of the metal increases. Therefore, the electron transfer between metal and boron is one of the key parameters to control the HER activity of MB₂. We have also recently found an unexpected lattice parameter-dependency on HER of ternary variants crystallizing with the AlB₂-type structure. Furthermore, an unexpected boron-chain dependency of the HER activity was discovered in the V-B system, that even allows for the prediction of unknow active HER catalysts. Using a recently developed synthesis, we were able to synthesize most transition metal borides at the nanoscale. Nanoscale VB₂ and CoB have indeed shown much improved HER activities if compared to their bulk counterparts.

Bioinorganic Chemistry Subdivision [since 1985]

Stephen J. Lippard (MIT), 1987 Subdivision Chair

“Metalloneurochemistry”

Metalloneurochemistry describes research at the interface of bioinorganic chemistry and neuroscience. This still young area of science comprises a wide range of topics whereby metal ions and complexes control or modify neurological functions. This lecture will focus on the control of sensory perception in mammals with a specific focus on audition, olfaction, and vision, as well as learning and memory.

Hannah Shafaat (Ohio State Univ.), 2022 Subdivision Chair

“Using protein-derived models to study small molecule activation in metalloenzymes: Putting the “bio” in bioinorganic”

Nature uses specialized metalloenzymes to carry out small molecule activation reactions, including proton reduction, CO₂ fixation, and O₂ activation, with unparalleled efficiency, rates, and selectivity. Reproducing both the activity and efficiency of metalloenzymes in sustainable anthropogenic systems remains one of the “holy grails” of inorganic chemistry., However, identifying the precise molecular components responsible for these desirable properties has been challenging in the natural metalloenzymes, hindering efforts to develop analogous processes in synthetic compounds. Considering the inherent complexity of a metalloenzyme and the many interactions, both strong and weak, that contribute to the function of an enzyme, we have elected to model natural metalloenzymes on a biochemical platform. Towards this end, we have developed structural, functional, and mechanistic mimics of the [NiFe] hydrogenase, carbon monoxide dehydrogenase (CODH), and acetyl coenzyme A synthase that are based within robust protein scaffolds. Our recent efforts to install and modulate novel reactivity in rubredoxin, ferredoxin, and azurin proteins will be discussed, along with findings from multiple complementary spectroscopic techniques used to probe the catalytic mechanisms. These engineered metalloenzymes provide direct insight into the fundamental chemical principles driving the natural systems and offer design principles for developing catalysts that utilize analogous principles.

Nanoscience Subdivision [since 2003]

Peidong Yang (UC Berkeley), 2003 Subdivision Chair

“Nanoscience subdivision, 18 years after”

18 years ago, when the nanoscience subdivision was established, one report in C&EN stated “In much of today’s scientific research, small is king”. It was at that time the Nanoscience Subdivision was established to create a new home for small-scale researchers. The subdivision emphasizes interest in fundamental chemistry issues that are central to advancing nanoscience and engineering, including the synthesis, characterization, physical and chemical properties of inorganic nanocrystals and inorganic-organic hybrid materials. At the inauguration symposium, I have said “This subdivision definitely has the potential to grow into a full-scale division.”<br/> <br/>For 18 years, we have witnessed explosive growth in nanoscience research. Even though the subdivision has not grown into a full-scale division as I have expected, its impact within the entire chemical community is arguably comparable to those of many traditional divisions. While the subdivision is housed within inorganic division, its influence goes well beyond inorganic and reaches almost every sub-discipline of chemistry. Due to highly interdisciplinary nature of nanoscience, it is almost impossible to cover every aspect of this exciting and rapidly-evolving field. We will take a brief historical look at the landscape and major milestones of nanoscience development by highlighting the publication trends, research funding supports, talent training and selected research breakthroughs. It goes without saying that “there is a great future in nanoscience!”

Raffaella Buonsanti (EPFL), 2022 Subdivision Chair

“Towards retrosynthesis of inorganic nanocrystals to advance catalysis and energy technologies”

Affordable clean energy and climate action are two of the sustainable development goals set by the United Nations to be achieved by 2030. The vast majority of energy technologies relies on nanomaterials and their progress is strongly connected to the ability of materials chemists to tune their property and function-dictating features (i.e. size, composition, composition, morphology). In this talk, I will present our recent group efforts towards the synthesis via colloidal chemistry of atomically defined nanocrystals (NCs) with properties of interest for energy conversion applications. The first part will be dedicated to our colloidal atomic layer deposition (c-ALD) method to grow tunable oxide shells around different inorganic NC cores. I will discuss the formation mechanism of the shell by sharing our recent insights into the surface chemistry. I will also demonstrate some of the enabled applications, such as the improved stability of the colloidal ink, which is particularly important in the context of quantum dot-based LEDs and solar cells, and the enhanced resistance against harsh environment, which is relevant for catalytic applications. The second part will focus on our studies on the synthesis development and formation mechanism of Cu NCs. I will illustrate how these NCs with precisely tunable shapes, sizes and interfaces serve as ideal platforms to advance our current knowledge towards improved selectivity in the electrochemical CO2 reduction reaction. Finally, I will share our results evidencing that these NCs can sustain their catalytic activity and selectivity at technologically relevant conditions, therefore might also offer practical solutions.

Afternoon Session Andy Borovik, presiding

Coordination Chemistry Subdivision [since 2013]

Kristin Bowman-James (Univ. Kansas), 2013 Subdivision Chair

“Coordination chemistry, approaching 125 years and still driving fast”

Coordination chemistry had its beginnings almost 50 years before inorganic chemistry became an ACS Division, courtesy of the brilliant Nobel Laureate Alfred Werner. When the Division of Inorganic Chemistry (DIC) was inaugurated, coordination chemistry played a major role. Different areas of inorganic chemistry soon began to grow, and although it was controversial at the time, subdivisions were created. Then, 100 years after the Nobel Prize in Chemistry for Coordination Chemistry in 1913, coordination chemistry was awarded its own subdivision. This talk will highlight the travels of coordination chemistry along the way to its long-awaited recognition as a subdivision.

Trevor Hayton (UC Santa Barbara), 2022 Subdivision Chair

“Werner we go from here? Coordination Chemistry in the Next 65 Years”

This talk will discuss the latest trends in coordination chemistry, with a particular focus on the use of coordination complexes as single molecule magnets, qubits, and nuclear medicine therapeutics, as well as their use in nanoscience. These cutting-edge applications reveal the inherent promise in coordination chemistry and suggest that coordination complexes will feature an important role in science and technology in the coming decades.

Sustainable Energy and the Environment (SEE) [since 2017]

Cliff Kubiak (UC San Diego), 2017 Subdivision Chair

“It is the newest Subdivision of the DIC, SEE?”

The newest Subdivision of the ACS Division of Inorganic Chemistry is Sustainability, Energy and Environment (SEE) which was envisioned by DIC Chair Claudia Turro and the Executive Committee in 2016. SEE was launched in 2017, and the author of this abstract was elected Subdivision Chair. This lecture will review the brief history of SEE, the role that it plays, and opportunities that it provides to inorganic chemists in the fast-moving field of research in energy conversion, sustainable chemistry, and environmental chemistry.

Jenny Yang (UC Irvine), 2022 Subdivision Chair

“The critical role of inorganic chemistry for sustainable energy and environment”

Within a century, technological and industrial advancements have resulted in transformative improvements to our quality of life and standards of living. However, many of our current technologies are unsustainable and/or result in pollution to our planet’s air and water, resulting in dramatic changes to our ecosystems that are unprecedented in human history. Inorganic chemistry can play a key role in advancing the fundamental and applied science required for new, more sustainable technology or to address current environmental concerns. A selection of potential research areas and directions relevant to sustainable energy and environmental remediation will be discussed.

Inorganic Chemistry

Alison Butler (UC Santa Barbara), DIC Chair 2021

Introduction

Bill Tolman (Washington Univ., St. Louis), Editor-in-Chief, Inorganic Chemistry

“Reflections on Inorganic Chemistry: the Journal and the Field it Chronicles”

Birthdays offer an opportunity to celebrate a life well-lived as well as a chance to plan for the future. The journal Inorganic Chemistry just turned 60, and alongside the Division of Inorganic Chemistry, has evolved during its lifetime, always reflecting what the community views as exciting science. The diversity of the science chronicled in Inorganic Chemistry is particularly striking, and the impacts of the discoveries and analyses published over the many decades are myriad. In this lecture, we look back at the long life of our flagship journal and then forward to what might come next, in celebration and with the hope of inspiring the next generations who tackle exciting chemistry challenges that span the entire periodic table.

POSTER SESSION: Mid/Late Afternoon with Poster Awards