Most favorable cumulenic structures in iron-capped linear carbon chains are short singlet odd-carbon dications: a theoretical view

Literature Information

Publication Date 2018-05-21
DOI 10.1039/C7CP08673C
Impact Factor 3.676
Authors

Liang Pu, Zhong Zhang, R. Bruce King, Wesley D. Allen


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Abstract

Iron-capped, linear-carbon-chain dications have been investigated at the M06L/DZP level of quantum chemistry in order to determine their structural and electronic properties, focusing on differences between chains containing odd and even numbers of carbon atoms. Such differences result from changes in the electronic states and the acetylenic or cumulenic nature of the carbon chain. Interestingly, the short even-carbon chains exhibit distinct properties, but upon chain lengthening undergo a transition to structures similar to those of odd-carbon chains, with a turning point around [FeC10Fe]2+. On the other hand, the less extensively investigated short odd-carbon chains, such as [FeC5Fe]2+, [FeC7Fe]2+ and [FeC9Fe]2+, due to synthetic difficulty, are predicted to exhibit more exceptional properties than the short even-carbon chains in every aspect, such as excellent back bonding as well as more cumulenic and more nearly linear structures. This theoretical study suggests that more experimental work should be considered on metal-capped, short linear odd-carbon chains as potential building blocks for novel electronic and optical materials.

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DOI: 10.1039/C5CP90016F

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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