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Why Do B–P and Al–P Polymers Differ? Structures, Stability, and Electronic Properties of Chain and Ring [H 2 PEH 2 ] n Oligomers (E=B, Al; n =1 – 15)
Author(s) -
Pomogaeva Anna V.,
Scheer Manfred,
Timoshkin Alexey Y.
Publication year - 2018
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.201803008
Subject(s) - delocalized electron , chain (unit) , ring (chemistry) , homo/lumo , oligomer , chemistry , crystallography , molecular orbital , stereochemistry , molecule , polymer chemistry , physics , organic chemistry , astronomy
Chain and ring [H 2 PEH 2 ] 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 [H 2 PBH 2 ] 15 and more than 5 eV for the ring isomer [H 2 PEH 2 ] 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.