Single vibronic level emission spectroscopic studies of the ground state energy levels and molecular structures of jet-cooled HGeBr, DGeBr, HGeI, and DGeI

Single vibronic level dispersed fluorescence spectra of jet-cooled HGeBr, DGeBr, HGeI, and DGeI have been obtained by laser excitation of selected bands of the A (1)A(")-X (1)A(') electronic transition. The measured ground state vibrational intervals were assigned and fitted to anharmonicity expressions, which allowed the harmonic frequencies to be determined for both isotopomers. In some cases, lack of a suitable range of emission data necessitated that some of the anharmonicity constants and vibrational frequencies be estimated from those of HGeClDGeCl and the corresponding silylenes (HSiX). Harmonic force fields were obtained for both molecules, although only four of the six force constants could be determined. The ground state effective rotational constants and force field data were combined to calculate average (r(z)) and approximate equilibrium (r(e) (z)) structures. For HGeBr r(e) (z)(GeH)=1.593(9) A, r(e) (z)(GeBr)=2.325(21) A, and the bond angle was fixed at our CCSD(T)/aug-cc-pVTZ ab initio value of 93.6 degrees . For HGeI we obtained r(e) (z)(GeH)=1.589(1) A, r(e) (z)(GeI)=2.525(5) A, and bond angle=93.2 degrees . Franck-Condon simulations of the emission spectra using ab initio Cartesian displacement coordinates reproduce the observed intensity distributions satisfactorily. The trends in structural parameters in the halogermylenes and halosilylenes can be readily understood based on the electronegativity of the halogen substituent.     

Amino acid-derived enaminones: a study in ring formation providing valuable asymmetric synthons

A new reaction for the preparation of enaminones has been discovered. This method employs beta-amino acids as starting materials to allow diversification as well as incorporation of chirality. The beta-amino acids, once converted to ynones, are readily cyclized to the desired six-membered enaminone via a two-step, one-pot protocol. Although disguised as a 6-endo-dig cyclization, the reagents employed in the transformation play a direct role in bond making and bond breaking, thus changing the mode of addition.     

Integrating DEA-oriented performance assessment and target setting using interactive MOLP methods

Data envelopment analysis (DEA) and multiple objective linear programming (MOLP) are tools that can be used in management control and planning. Whilst these two types of model are similar in structure, DEA is directed to assessing past performances as part of management control function and MOLP to planning future performance targets. This paper is devoted to investigating equivalence models and interactive tradeoff analysis procedures in MOLP, such that DEA-oriented performance assessment and target setting can be integrated in a way that the decision makers’ preferences can be taken into account in an interactive fashion. Three equivalence models are investigated between the output-oriented dual DEA model and the minimax reference point formulations, namely the super-ideal point model, the ideal point model and the shortest distance model. These models can be used to support efficiency analysis in the same way as the conventional DEA model does and also support tradeoff analysis for setting target values by individuals or groups. A case study is conducted to illustrate how DEA-oriented efficiency analysis can be conducted using the MOLP methods and how such performance assessment can be integrated into an interactive procedure for setting realistic target values.     

On the incorporation of adversarial reasoning in course of action analysis and resource allocation

Course of Action analysis and Resource Management are concerned with the allocation of resources over time to effect desired actions as a result of the perceived situation awareness. Decision Support Systems provide automated recommended courses of action to decision makers, considering relevant resource capabilities and constraints. Incorporating potential adversary actions and reactions to the current course of action decision (and the resources effecting the actions) in the decision making process will make the decision support system more robust and increase confidence that the recommended decisions are appropriate responses to the unfolding situations. We discuss research results from the inclusion of possible adversary actions and reactions into the course of action/resource allocation decision making framework. The overall decision problem is formulated as a multi-stage mathematical program. As the problem is NP-hard, an heuristic is developed through a natural problem decomposition. Simulated results show the effectiveness of the heuristic in producing good-quality solutions in an efficient manner.     

Influence of atmospheric turbulence on states of light carrying orbital angular momentum

We have experimentally studied the degradation of mode purity for light beams carrying orbital angular momentum (OAM) propagating through simulated atmospheric turbulence. The turbulence is modeled as a randomly varying phase aberration, which obeys statistics postulated by Kolmogorov turbulence theory. We introduce this simulated turbulence through the use of a phase-only spatial light modulator. Once the turbulence is introduced, the degradation in mode quality results in crosstalk between OAM modes. We study this crosstalk in OAM for 11 modes, showing that turbulence uniformly degrades the purity of all the modes within this range, irrespective of mode number.     

An Efficient Approach to Large-Scale Ab Initio Conformational Energy Profiles of Small Molecules

Accurate conformational energetics of molecules are of great significance to understand maby chemical properties. They are also fundamental for high-quality parameterization of force fields. Traditionally, accurate conformational profiles are obtained with density functional theory (DFT) methods. However, obtaining a reliable energy profile can be time-consuming when the molecular sizes are relatively large or when there are many molecules of interest. Furthermore, incorporation of data-driven deep learning methods into force field development has great requirements for high-quality geometry and energy data. To this end, we compared several possible alternatives to the traditional DFT methods for conformational scans, including the semi-empirical method GFN2-xTB and the neural network potential ANI-2x. It was found that a sequential protocol of geometry optimization with the semi-empirical method and single-point energy calculation with high-level DFT methods can provide satisfactory conformational energy profiles hundreds of times faster in terms of optimization.     

Atypical “Masked” Frustrated Lewis Pair Character in a Geminal-Linked Phosphine-Borane

We report the synthesis and reactivity of the geminal-linked fluorene-derived P/B frustrated Lewis pair (FLP) ⁱPr₂P(C₁₃H₈)BCy₂ ( 1 ). Compound 1 displays anomalous behavior towards small molecules, acting as a “masked” FLP. This behavior stems from significant polarization of the B−C(fluorene) bond in 1 , as identified by density functional theory (DFT) computations. We exploit this B−C bond polarity through reactions with PhPCl₂, H₃N ⋅ BH₃, and ⁱPrNH₂, demonstrating P−Cl and N−H bond activation, respectively.     

Frustrated Lewis Pair Adduct of Atomic P(−1) as a Source of Phosphinidenes (PR), Diphosphorus (P2), and Indium Phosphide

We report phosphinidenes (PR) stabilized by an intramolecular frustrated Lewis pair (FLP) chelate. These adducts include the parent phosphinidene, PH, which is accessed via thermolysis of coordinated HPCO. The reported FLP-PH species acts as a springboard to other phosphorus-containing compounds, such as FLP-adducts of diphosphorus (P₂) and InP₃. Our new adducts participate in thermal- or light-induced phosphinidene elimination (of both PH and PR, R=organic group), transfer P₂ units to an organic substrate, and yield the useful semiconductor InP at only 110 °C from solution.     

Lewis Acid Supported Nickel Nitrenoids

Metalation of the polynucleating ligand ^F,tbsLH₆ (1,3,5-C₆H₉(NC₆H₃−4-F−2-NSiMe₂^tBu)₃) with two equivalents of Zn(N(SiMe₃)₂)₂ affords the dinuclear product (^F,tbsLH₂)Zn₂ ( 1 ), which can be further deprotonated to yield (^F,tbsL)Zn₂Li₂(OEt₂)₄ ( 2 ). Transmetalation of 2 with NiCl₂(py)₂ yields the heterometallic, trinuclear cluster (^F,tbsL)Zn₂Ni(py) ( 3 ). Reduction of 3 with KC₈ affords [KC₂₂₂][(^F,tbsL)Zn₂Ni] ( 4 ) which features a monovalent Ni centre. Addition of 1-adamantyl azide to 4 generates the bridging μ³-nitrenoid adduct [K(THF)₃][(^F,tbsL)Zn₂Ni(μ³-NAd)] ( 5 ). EPR spectroscopy reveals that the anionic cluster possesses a doublet ground state (S = ). Cyclic voltammetry of 5 reveals two fully reversible redox events. The dianionic nitrenoid [K₂(THF)₉][(^F,tbsL)Zn₂Ni(μ³-NAd)] ( 6 ) was isolated and characterized while the neutral redox isomer was observed to undergo both intra- and intermolecular H-atom abstraction processes. Ni K-edge XAS studies suggest a divalent oxidation state for the Ni centres in both the monoanionic and dianionic [Zn₂Ni] nitrenoid complexes. However, DFT analysis suggests Ni-borne oxidation for 5 .     

Fluorogenic Photo-Crosslinking of Glycan-Binding Protein Recognition Using a Fluorinated Azido-Coumarin Fucoside

Glycan recognition by glycan-binding proteins is central to the biology of all living organisms. The efficient capture and characterization of relatively weak non-covalent interactions remains an important challenge in various fields of research. Photoaffinity labeling strategies can create covalent bonds between interacting partners, and photoactive scaffolds such as benzophenone, diazirines and aryl azides have proved widely useful. Since their first introduction, relatively few improvements have been advanced and products of photoaffinity labeling remain difficult to detect. We report a fluorinated azido-coumarin scaffold which enables photolabeling under fast and mild activation, and which can leave a fluorescent tag on crosslinked species. Coupling this scaffold to an α-fucoside, we demonstrate fluorogenic photolabeling of glycan-protein interactions over a wide range of affinities. We expect this strategy to be broadly applicable to other chromophores and we envision that such “fluoro-crosslinkers” could become important tools for the traceable capture of non-covalent binding events.