Research

Automated reaction path network exploration and product identification through kinetic analysis are essential for mimicking reaction vessels. Common practice employs less expensive semi-empirical methods for initial exploration with energy refinement using accurate density functional theory (DFT) methods. However, semi-empirical methods often lead to less accurate reaction kinetics, therefore, not suitable for efficient exploration and product predictions. We demonstrate the benefit of iterative training of a delta-learning neural network potential (ΔNNP) for automated reaction path explorations, here, ethylene polymerization catalyzed by [ZrCp2CH3]+ catalyst and [B(C6F5)4]⁻ cocatalyst, achieving DFT-level accuracy through a delta-learning between DFT and semi-empirical levels. This approach thus allows the model to tackle increasingly complex reactions, an important step towards mimicking reaction vessels.

Reference: 

ChemRxiv 2025; DOI: 10.26434/chemrxiv-2025-5vj39 

Heteropolar two-dimensional materials, including hBN, are promising candidates for seawater desalination and osmotic power harvesting. We showed a multiscale simulation strategy to develop high-fidelity force fields (FF) for H- and OH-functionalized hexagonal boron nitride (hBN) nanopores. Our density functional theory (DFT)-based ab initio MD simulations of hBN nanopores surrounded by water molecules reveal a high propensity for hydrogen (H) and hydroxyl (OH) and oxygen (O) functionalization at the edges, highlighting a route to tune membranes. Our work is expected to enable the realistic modeling of edge-functionalized hBN in aqueous media for various application areas.

Reference:

J. Chem. Phys. 2025, 162 (4), 044705; DOI: 10.1063/5.0242541

We show the interrelationships among three apparently unrelated, parallel fields of boron chemistry practiced in very different experimental conditions i.e. in solution, gas phase and solid by finding common threads or converging points with a variety of novel bonding concepts. Such convergence of thought, bridging many areas, results in attractive novel ideas not accessible/thought of otherwise. The strategy of a molecules to materials continuum in the field of boron chemistry, was drawn through the stabilization of an interlocked boron wheel Mn2B10H10 having Möbius aromaticity, Hückel aromatic metal-doped boranaphthalene M2@B10H8 and M2B5 2D-sheets (M = Mn and Fe). 

Reference:

Chem. Sci., 2022, 13 (31), 8968-8978; DOI: 10.1039/D2SC02244C

Two important strategies, use of transition-metal templates and Lewis donor ligands have been employed to stabilize otherwise unstable boron complexes. Incorporation of a group IV metal fragment, ZrCp2, into a borocycle is an effective strategy to stabilize a B≡B triple bond in a cyclic system by donating two electrons to the central BB unit. Binuclear tantalum template stabilizes a classical [B2H5]− ion due to the stabilization of sp2-B center by electron donation from tantalum. Strong σ-donating phosphine ligands (L) stabilize donor–acceptor bonding interaction in gem-diborene L2B-BBr2. 

References:

Isr. J. Chem., 2022, 62 (1-2), e202100114; DOI: 10.1002/ijch.202100114

Angew. Chem. Int. Ed., 2019, 58, 17684-17689;  DOI: 10.1002/anie.201911480

Angew. Chem. Int. Ed., 2018, 57, 8079-8083; DOI: 10.1002/anie.201803154

Chem. Eur. J., 2017, 23 (41), 9746-9751; DOI: 10.1002/chem.201702422

Although product distributions of spin-forbidden ion–molecule reactions in the gas phase have been extensively studied, investigations into how product distributions depend on spin state in solution are still relatively rare. In this work, we explored a unique isocyanide coupling reaction mediated by a Cr–Cr quintuple-bonded complex, which yields products with different spin multiplicities. This system provided an opportunity to computationally investigate the electronic structures of the spin-state-dependent products, their mechanistic formation pathways, and the minimum energy crossing points (MECPs) connecting different spin surfaces. The approach employed—explicitly involving multiple potential energy surfaces—offers a framework that is readily extendable to other spin-dependent solution-phase transformations.

Reference:

Organometallics, 2020, 39 (10), 1700-1709; DOI: 10.1021/acs.organomet.9b00841

Product distributions of reductive coupling of isocyanide and CO mediated by a Cr–Cr quintuple bonded complex and B–B multiple bonded complexes are controlled by in donor–acceptor bonding. In the case of CO, the Cr–Cr quintuple bonded complex is unable to show C–C coupling due to the high π- back bonding possibility of CO whereas, in the case of isocyanide, less π- back bonding possibility allows the reactions to undergo a spin transition and gives a series of products with different spin multiplicities. Similarly, reactions of B–B multiple bonded complexes with CO and isocyanides are also controlled by donor–acceptor capabilities of ligands, and the C–C coupling takes place by changing the oxidation state of the boron centers from +I to +II, in contrast to the classical main group mediated reactions where stable oxidation states are always preserved. 

Reference:

J. Phys. Chem. A, 2021, 125 (33), 7207-7216; DOI: 10.1021/acs.jpca.1c05185