NDLI: Variations of bistricyclic aromatic enes: mono-bridged tetraarylethene naphthologs

Content Provider	Springer Nature Link
Author	Assadi, Naela Pogodin, Sergey Cohen, Shmuel Agranat, Israel
Copyright Year	2014
Abstract	The syntheses, molecular and crystal structures, NMR spectroscopic study, and DFT computational study of naphthologs of mono-bridged (X = –, O, S, Se, and Te) tetraarylethene (BAE-1s) 11–25 with α,α-, β,β-, and α,β-dinaphthalenyl substituents have been reported. The BAE-1s have been prepared by Barton–Kellog twofold extrusion from the respective chalcogenothiones and diazomethylenebisnaphthylenes. Complete assignments of $^{1}$H- and $^{13}$C-NMR spectra of 11–25 have been made through 2-dimensional correlation spectroscopy (DQF-COSY, HSQC, HMBC, and NOESY). The corresponding intermediates, thiiranes 33–47, have been also isolated (except 38), and their molecular and crystal structures have been determined. The molecular structures of BAE-1s 12–15, 20, and 22–25 adopted folded-twisted conformations with considerably folded (φ = 30°–57°) tricyclic moieties. The α,α- and α,β-dinaphthalenyl derivatives are more overcrowded than β,β-dinaphthalenyl derivatives. The relief of the steric strain due to the overcrowding around C$^{9}$ = C$^{9′}$ caused by the presence of naphthalenyl substituents was achieved by their twisting around the single bonds that connect the α-naphthalenyl and β-naphthalenyl moieties to C$^{9′}$. The $^{1}$H-NMR spectra have shown shielding of H$^{2}$, H$^{7}$ of 11–25 and the pronounced deshielding of H$^{8′}$, H$^{8″}$ of α,α-dinaphthalenyl-substituted BAE-1s 13–15 in contrast to β,β-dinaphthalenyl-substituted BAE-1s 16–20. The upfield shifts of H$^{2}$, H$^{7}$ suggested conformations in which these hydrogens are located above the planes of the opposing naphthalene rings. DFT calculations of 11–20 have been performed at B3LYP/6-31G(d) and B3LYP/SDD. The results have shown that the global minima of BAE-1s without a chalcogen bridge 11 and 16 are twisted (–sc,–sc)-C $_{2}$-t conformations. The global minima of BAE-1s with a chalcogen bridge are folded-twisted (–sc,–ac)-C $_{1}$-ft conformations for α,α-dinaphthalenyl-substituted BAE-1s 12–15 and either anti- or syn-(–sc,ac)-C $_{1}$-ft conformations for β,β-dinaphthalenyl-substituted BAE-1s 17–20. The pronounced differences between the α,α-dinaphthalenyl and the β,β-dinaphthalenyl derivatives are noted. Dispersion-corrected B3LYP calculations stabilize significantly the α,α-dinaphthalenyl derivatives versus the β,β-dinaphthalenyl derivatives. The geometrical parameters of BAEs-1 11–15 and 20, derived from their molecular X-ray structures and from their B3LYP-optimized geometries are in a good agreement.
Starting Page	319
Ending Page	352
Page Count	34
File Format	PDF
ISSN	10400400
Journal	Structural Chemistry
Volume Number	26
Issue Number	1
e-ISSN	15729001
Language	English
Publisher	Springer US
Publisher Date	2014-08-28
Publisher Place	Boston
Access Restriction	One Nation One Subscription (ONOS)
Subject Keyword	Naphthalene Te Se Overcrowding Conformations AIE luminogen DFT NMR Empirical dispersion correction Computer Applications in Chemistry Physical Chemistry Theoretical and Computational Chemistry
Content Type	Text
Resource Type	Article
Subject	Physical and Theoretical Chemistry Condensed Matter Physics

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