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The coupling interactions of nuclei across four or more bonds are usually weak, with J values less than 1 Hz. While these are usually not observed in spectra, the presence of multiple bonds along the coupling pathway can result in observable long-range coupling.
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Halogenation is another class of electrophilic addition reactions where a halogen molecule gets added across a π bond. In alkynes, the presence of two π bonds allows for the addition of two equivalents of halogens (bromine or chlorine). The addition of the first halogen molecule forms a trans-dihaloalkene as the major product and the cis isomer as the minor product. Subsequent addition of the second equivalent yields the tetrahalide.
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Alkynes are unsaturated hydrocarbons characterized by the presence of carbon-carbon triple bonds and have a general formula CnH2n-2. The nomenclature of alkynes follows a set of rules similar to alkanes and alkenes; however, alkynes bear the suffix "-yne" instead of "-ane" or "-ene." There are two approaches to naming alkynes:
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Do quantum interference effects manifest in acyclic aliphatic molecules with anchoring groups?

Ravinder Kumar1, Charu Seth2, Ravindra Venkatramani1

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This study reveals how quantum interference (QI) from anchoring groups, not just molecular backbones, can control single-molecule electronic conductance. These findings apply to simple aliphatic molecules and suggest mechanical tuning for molecular electronics.

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Area of Science:

  • Molecular electronics
  • Quantum interference phenomena
  • Single-molecule devices

Background:

  • Controlling single-molecule electronic conductance is crucial for molecular electronics applications like insulation, switching, and energy conversion.
  • Quantum interference (QI) effects are typically manipulated by altering molecular structure or anchoring group positions.
  • Previous research primarily focused on QI within sigma and/or pi channels of molecular backbones, often in conjugated or cyclic systems.

Purpose of the Study:

  • To demonstrate that QI effects originating from anchoring group interactions can be utilized to design single-molecule electronic devices.
  • To show that QI can be harnessed in simple acyclic aliphatic systems, expanding beyond conjugated/cyclic structures.
  • To explore the potential of mechanical stimuli for tuning charge transport properties in single molecules.

Main Methods:

  • Investigated quantum interference (QI) effects in single molecular junctions.
  • Analyzed electronic transmission spectra of alkanedithiols, alkanediamines, and alkanediselenols.
  • Identified band gap state resonances and anchoring group-sensitive QI phenomena.

Main Results:

  • Demonstrated that QI effects from anchoring group interactions can control electronic conductance in single molecules.
  • Showcased the applicability of QI in simple acyclic aliphatic systems.
  • Identified resonances in transmission spectra dependent on chain length and anchoring groups.
  • Observed QI between molecular orbitals localized on anchoring groups.

Conclusions:

  • Single-molecule electronic devices can be designed based on QI effects from anchoring group interactions.
  • QI effects are harnessable in simple aliphatic molecules, broadening their application scope.
  • Predicted that mechanical stimuli can tune charge transport properties in break-junction experiments by leveraging these QI features.