Properties of gaseous closo-[B6X6]2− dianions (X = Cl, Br, I)

Rohdenburg, Markus; Yang, Zhenhua; Su, Pei; Bernhardt, Eduard; Yuan, Qinqin; Aprà, Edoardo; Grabowsky, Simon; Laskin, Julia; Jenne, Carsten; Wang, Xue‐Bin; Warneke, Jonas

doi:10.1039/d0cp02581j

Cited by 13 publications

(25 citation statements)

References 73 publications

(77 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Theoretical evaluations of the RCB height were performed along three different directions, including those along and perpendicular to the line defined by the center of mass and N – from which H + is eliminated, and perpendicular to the nucleobase ring plane (for the definition of these directions, see Figure S6). Both the electrostatic potential (ESP) and point charge method (PCM), two methods commonly used in previous studies, − are visualized in Figure and summarized in Table . The electron detachment pathway perpendicular to the nucleobase ring plane based on the PCM model predicts RCBs that match the experimental trend, i.e., 1.54/2.0, 1.46/2.0, 1.66/2.5, and 1.65/2.5 for theoretical/experimental RCBs of [dAMP-2H] 2– , [dGMP-2H] 2– , [dCMP-2H] 2– , and [dTMP-2H] 2– , respectively.…”

mentioning

confidence: 99%

Photoelectron Spectroscopy and Theoretical Investigations of Gaseous Doubly Deprotonated 2′-Deoxynucleoside 5′-Monophosphate Dianions

Yuan

Chomicz-Mańka

Makurat

et al. 2021

J. Phys. Chem. Lett.

Self Cite

View full text Add to dashboard Cite

A better understanding of the mechanism of oxidative DNA damage requires obtaining a molecular level description of nucleotides in various charge states. Herein, we report a systematic photoelectron spectroscopy and theoretical investigation of the electronic and geometric structures of four doubly deprotonated 2′-deoxynucleoside 5′-monophosphate dianions, the smallest quintessential DNA building block. These dianions are intrinsically stable with their adiabatic/vertical detachment energies (ADE/VDE) ranging from 0.85/1.07 (A) and 1.05/1.30 (G) to 1.20/1.50 (C) and 1.80/2.10 eV (T). The repulsive Coulomb barrier against electron detachment is 2.0 eV for purines and 2.5 eV for pyrimidines. Dianions are deprotonated at the phosphate group and the amino group of a nucleobase. The πtype HOMO orbital resides on the nucleobase moiety for each dianion. This spatial distribution of HOMO suggests that the most loosely bound electron is detached along the direction perpendicular to the nucleobase. When combined with the previous results, this work makes complete the depiction of basic building blocks of DNA at the molecular level.

show abstract

mentioning

confidence: 99%

Photoelectron Spectroscopy and Theoretical Investigations of Gaseous Doubly Deprotonated 2′-Deoxynucleoside 5′-Monophosphate Dianions

Yuan

Chomicz-Mańka

Makurat

et al. 2021

J. Phys. Chem. Lett.

Self Cite

View full text Add to dashboard Cite

show abstract

“…As an example for photoelectron spectroscopy of closo-borate dianions, Figure 2a shows the spectrum of [closo-B 6 Br 6 ] 2− measured with a 157 nm laser. 24 Four spectral bands A−D in the electron binding energy (EBE) range from 0.5 to 5.0 eV are observed. These bands are assigned to the transitions from the electronic ground state of the [B 6 Br 6 ] 2− dianion to the ground and excited electronic states of the singly charged [B 6 Br 6 ] •− anion.…”

Section: Resultsmentioning

confidence: 99%

Measuring Electronic Structure of Multiply Charged Anions to Understand Their Chemistry: A Case Study on Gaseous Polyhedral closo-Borate Dianions

Warneke

Wang

2021

J. Phys. Chem. A

Self Cite

View full text Add to dashboard Cite

Research on multiply charged anions (MCAs) in the gas phase has been intensively performed during the past decades, mainly to understand fundamental molecular physics phenomena, for example, intramolecular Coulomb repulsion and existence of the repulsive Coulomb barrier. However, the relevance of these investigations with respect to understanding MCAs’ chemistry appears often vague. Here, we discuss how insights into the electronic structure obtained from negative ion photoelectron spectroscopy (NIPES) combined with theoretical calculations and collision-induced dissociation can provide a fundamental understanding of the intrinsic chemical reactivity of MCAs and their fragments. This is exemplified in our studies on polyhedral closo-borate dianions [B n X n ]2– (n = 6, 10, 11, 12; X = H, F–I, CN) and their fragment ions. For example, the rational design of closo-borate dianions with specific electronic properties is described, which leads to generating highly reactive fragments. Depending on the dianionic precursor, these fragments are tuned to either bind noble gases effectively or activate small molecules like CO and N2. The intrinsic electronic properties of closo-borate dianions are further compared to their electrochemistry in solutions, revealing solvent effects on the redox potentials. Neutral host molecules such as cyclodextrins are found to bind strongly to [B n X n ]2–, and gas phase NIPES provides insights into the intrinsic host–guest interactions. Finally, outlooks including the direct NIPES of molecular fragment ions that cannot be generated in the condensed phase and their utilization in preparative mass spectrometry are discussed.

show abstract

“…Very useful experimental technique to probe the properties of gaseous multiply charged anions is photoelectron spectroscopy, which provides direct measurements of the excess electron binding energies (BE), allowing information about stability of those anions 45 . Recently, the joint experimental and theoretical investigations of the dianions, B 6 X 6 2− and B 12 X 12 2− , (X = F, Cl, Br, I, At), with some surprising properties, have helped expanding our understanding of the fundamental physics of multiply charged anions 46,47 …”

Section: Resultsmentioning

confidence: 99%

Small lithium‐chloride clusters: Superalkalis, superhalogens, supersalts and nanocrystals

Milovanović

2021

J Comput Chem

View full text Add to dashboard Cite

In the present paper, the results of the theoretical investigation of the small lithium‐chloride clusters are reported. The geometrical structures, electronic and thermodynamic stability of superalkalis, superhalogens, and their single and double charged ions are obtained using efficient and accurate quantum chemistry methods. Further, low‐lying isomers of the LinCln (n=2−5) clusters and their stability parameters are calculated. Two ways of formation of the LinCln clusters, polymerization of LiCl fragments and combination of superalkalis and superhalogen clusters, are compared. By examination the lattice energy and the average Li‐Cl bond length in rectangular LinCln (n≤60) clusters, it was concluded that already 50 LiCl are enough to mostly resembles the structure and stability of the bulk LiCl.

show abstract

Properties of gaseous closo-[B₆X₆]²⁻ dianions (X = Cl, Br, I)

Abstract: The electronic properties, fragmentation by collision-induced dissociation and bond properties of gaseous closo-[B6X6]2− (X = Cl, Br, I) dianions are discussed and compared to their larger-sized [B12X12]2− analogues.

Cited by 13 publications

References 73 publications

Photoelectron Spectroscopy and Theoretical Investigations of Gaseous Doubly Deprotonated 2′-Deoxynucleoside 5′-Monophosphate Dianions

Photoelectron Spectroscopy and Theoretical Investigations of Gaseous Doubly Deprotonated 2′-Deoxynucleoside 5′-Monophosphate Dianions

Measuring Electronic Structure of Multiply Charged Anions to Understand Their Chemistry: A Case Study on Gaseous Polyhedral closo-Borate Dianions

Small lithium‐chloride clusters: Superalkalis, superhalogens, supersalts and nanocrystals

Contact Info

Product

Resources

About