Why Do B–P and Al–P Polymers Differ? Structures, Stability, and Electronic Properties of Chain and Ring [H2PEH2]n Oligomers (E=B, Al; n=1–15)

Anna V. Pomogaeva, Manfred Scheer, Alexey Y. Timoshkin

Research output

Abstract

Chain and ring [H2PEH2]n oligomers (E=B, Al; n=2–15) have been computationally studied at the B3LYP/def2-TZVP level of theory. A strong tendency to cyclization was found for the chain Al–P oligomers with n>7, whereas analogous long B–P oligomers can exist as chain structures. Subsequent oligomerization enthalpies approach each other very closely for the ring and chain oligomers with an increase of n. However, these oligomers have very different electronic properties with band gaps below 0.2 eV for the chain [H2PBH2]15 and more than 5 eV for the ring isomer [H2PEH2]15. The molecular orbitals in the ring oligomers are highly delocalized, whereas for the chain isomers, the HOMO and LUMO are localized at the different ends of the oligomeric chain.

Original languageEnglish
Pages (from-to)17046-17054
Number of pages9
JournalChemistry - A European Journal
Volume24
Issue number64
DOIs
Publication statusPublished - 24 Oct 2018

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Oligomers
Electronic properties
Polymers
Isomers
Oligomerization
Cyclization
Molecular orbitals
Enthalpy
Energy gap

Scopus subject areas

  • Inorganic Chemistry

Cite this

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title = "Why Do B–P and Al–P Polymers Differ? Structures, Stability, and Electronic Properties of Chain and Ring [H2PEH2]n Oligomers (E=B, Al; n=1–15)",
abstract = "Chain and ring [H2PEH2]n oligomers (E=B, Al; n=2–15) have been computationally studied at the B3LYP/def2-TZVP level of theory. A strong tendency to cyclization was found for the chain Al–P oligomers with n>7, whereas analogous long B–P oligomers can exist as chain structures. Subsequent oligomerization enthalpies approach each other very closely for the ring and chain oligomers with an increase of n. However, these oligomers have very different electronic properties with band gaps below 0.2 eV for the chain [H2PBH2]15 and more than 5 eV for the ring isomer [H2PEH2]15. The molecular orbitals in the ring oligomers are highly delocalized, whereas for the chain isomers, the HOMO and LUMO are localized at the different ends of the oligomeric chain.",
keywords = "density functional calculations, donor–acceptor systems, electronic structures, oligomerization, phosphanylalane, phosphanylborane",
author = "Pomogaeva, {Anna V.} and Manfred Scheer and Timoshkin, {Alexey Y.}",
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T1 - Why Do B–P and Al–P Polymers Differ? Structures, Stability, and Electronic Properties of Chain and Ring [H2PEH2]n Oligomers (E=B, Al; n=1–15)

AU - Pomogaeva, Anna V.

AU - Scheer, Manfred

AU - Timoshkin, Alexey Y.

PY - 2018/10/24

Y1 - 2018/10/24

N2 - Chain and ring [H2PEH2]n oligomers (E=B, Al; n=2–15) have been computationally studied at the B3LYP/def2-TZVP level of theory. A strong tendency to cyclization was found for the chain Al–P oligomers with n>7, whereas analogous long B–P oligomers can exist as chain structures. Subsequent oligomerization enthalpies approach each other very closely for the ring and chain oligomers with an increase of n. However, these oligomers have very different electronic properties with band gaps below 0.2 eV for the chain [H2PBH2]15 and more than 5 eV for the ring isomer [H2PEH2]15. The molecular orbitals in the ring oligomers are highly delocalized, whereas for the chain isomers, the HOMO and LUMO are localized at the different ends of the oligomeric chain.

AB - Chain and ring [H2PEH2]n oligomers (E=B, Al; n=2–15) have been computationally studied at the B3LYP/def2-TZVP level of theory. A strong tendency to cyclization was found for the chain Al–P oligomers with n>7, whereas analogous long B–P oligomers can exist as chain structures. Subsequent oligomerization enthalpies approach each other very closely for the ring and chain oligomers with an increase of n. However, these oligomers have very different electronic properties with band gaps below 0.2 eV for the chain [H2PBH2]15 and more than 5 eV for the ring isomer [H2PEH2]15. The molecular orbitals in the ring oligomers are highly delocalized, whereas for the chain isomers, the HOMO and LUMO are localized at the different ends of the oligomeric chain.

KW - density functional calculations

KW - donor–acceptor systems

KW - electronic structures

KW - oligomerization

KW - phosphanylalane

KW - phosphanylborane

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