skip to main content

Title: Noncovalent bond between tetrel π-hole and hydride
The π-hole above the plane of the X 2 T′Y molecule (T′ = Si, Ge, Sn; X = F, Cl, H; Y = O, S) was allowed to interact with the TH hydride of TH(CH 3 ) 3 (T = Si, Ge, Sn). The resulting TH⋯T′ tetrel bond is quite strong, with interaction energies exceeding 30 kcal mol −1 . F 2 T′O engages in the strongest such bonds, as compared to F 2 T′S, Cl 2 T′O, or Cl 2 T′S. The bond weakens as T′ grows larger as in Si > Ge > Sn, despite the opposite trend in the depth of the π-hole. The reverse pattern of stronger tetrel bond with larger T is observed for the Lewis base TH(CH 3 ) 3 , even though the minimum in the electrostatic potential around the H is nearly independent of T. The TH⋯T′ arrangement is nonlinear which can be understood on the basis of the positions of the extrema in the molecular electrostatic potentials of the monomers. The tetrel bond is weakened when H 2 O forms an O⋯T′ tetrel bond with the second π-hole of F 2 T′O, and strengthened if H 2 O participates in an more » OH⋯O H-bond. « less
Authors:
; ; ;
Award ID(s):
1954310
Publication Date:
NSF-PAR ID:
10326160
Journal Name:
Physical Chemistry Chemical Physics
Volume:
23
Issue:
17
Page Range or eLocation-ID:
10536 to 10544
ISSN:
1463-9076
Sponsoring Org:
National Science Foundation
More Like this
  1. Molecules of the type XYT = Ch (T = C, Si, Ge; Ch = S, Se; X,Y = H, CH3, Cl, Br, I) contain a σ-hole along the T = Ch bond extension. This hole can engage with the N lone pair of NCH and NCCH3 so as to form a chalcogen bond. In the case of T = C, these bonds are rather weak, less than 3 kcal/mol, and are slightly weakened in acetone or water. They owe their stability to attractive electrostatic energy, supplemented by dispersion, and a much smaller polarization term. Immersion in solvent reverses the electrostatic interaction to repulsive, while amplifying the polarization energy. The σ-holes are smaller for T = Si and Ge, even negative in many cases. These Lewis acids can nonetheless engage in a weak chalcogen bond. This bond owes its stability to dispersion in the gas phase, but it is polarization that dominates in solution.
  2. A gr e at d e al of i nt er e st s urr o u n d s t h e u s e of tr a n s cr a ni al dir e ct c urr e nt sti m ul ati o n (t D C S) t o a u g m e nt c o g niti v e tr ai ni n g. H o w e v er, eff e ct s ar e i n c o n si st e nt a cr o s s st u di e s, a n d m et aa n al yti c e vi d e n c e i s mi x e d, e s p e ci all y f o r h e alt h y, y o u n g a d ult s. O n e m aj or s o ur c e of t hi s i n c o n si st e n c y i s i n di vi d u al diff er e n c e s a m o n g t h e pmore »arti ci p a nt s, b ut t h e s e diff er e n c e s ar e r ar el y e x a mi n e d i n t h e c o nt e xt of c o m bi n e d tr ai ni n g/ sti m ul ati o n st u di e s. I n a d diti o n, it i s u n cl e ar h o w l o n g t h e eff e ct s of sti m ul ati o n l a st, e v e n i n s u c c e s sf ul i nt er v e nti o n s. S o m e st u di e s m a k e u s e of f oll o w- u p a s s e s s m e nt s, b ut v er y f e w h a v e m e a s ur e d p erf or m a n c e m or e t h a n a f e w m o nt hs aft er a n i nt er v e nti o n. H er e, w e utili z e d d at a fr o m a pr e vi o u s st u d y of t D C S a n d c o g niti v e tr ai ni n g [ A u, J., K at z, B., B u s c h k u e hl, M., B u n arj o, K., S e n g er, T., Z a b el, C., et al. E n h a n ci n g w or ki n g m e m or y tr ai ni n g wit h tr a n scr a ni al dir e ct c urr e nt sti m ul ati o n. J o u r n al of C o g niti v e N e u r os ci e n c e, 2 8, 1 4 1 9 – 1 4 3 2, 2 0 1 6] i n w hi c h p arti ci p a nts tr ai n e d o n a w or ki n g m e m or y t as k o v er 7 d a y s w hil e r e c ei vi n g a cti v e or s h a m t D C S. A n e w, l o n g er-t er m f oll o w- u p t o a ss es s l at er p erf or m a n c e w a s c o n d u ct e d, a n d a d diti o n al p arti ci p a nt s w er e a d d e d s o t h at t h e s h a m c o n diti o n w a s b ett er p o w er e d. W e a s s e s s e d b a s eli n e c o g niti v e a bilit y, g e n d er, tr ai ni n g sit e, a n d m oti v ati o n l e v el a n d f o u n d si g nifi c a nt i nt er a cti o ns b et w e e n b ot h b as eli n e a bilit y a n d m oti v ati o n wit h c o n diti o n ( a cti v e or s h a m) i n m o d els pr e di cti n g tr ai ni n g g ai n. I n a d diti o n, t h e i m pr o v e m e nt s i n t h e a cti v e c o nditi o n v er s u s s h a m c o n diti o n a p p e ar t o b e st a bl e e v e n a s l o n g a s a y e ar aft er t h e ori gi n al i nt er v e nti o n. ■« less
  3. The tetrel bond (TB) recruits an element drawn from the C, Si, Ge, Sn, Pb family as electron acceptor in an interaction with a partner Lewis base. The underlying principles that explain this attractive interaction are described in terms of occupied and vacant orbitals, total electron density, and electrostatic potential. These principles facilitate a delineation of the factors that feed into a strong TB. The geometric deformation that occurs within the tetrel-bearing Lewis acid monomer is a particularly important issue, with both primary and secondary effects. As a first-row atom of low polarizability, C is a reluctant participant in TBs, but its preponderance in organic and biochemistry make it extremely important that its potential in this regard be thoroughly understood. The IR and NMR manifestations of tetrel bonding are explored as spectroscopy offers a bridge to experimental examination of this phenomenon. In addition to the most common σ-hole type TBs, discussion is provided of π-hole interactions which are a result of a common alternate covalent bonding pattern of tetrel atoms.
  4. The possibility of the transfer of the TH 3 group across a tetrel bond is considered by ab initio calculations. The TB is constructed by pairing PhTH 3 (Ph = phenyl; T = Si and Ge) with bases NH 3 , NHCH 2 , and the C 3 N 2 H 4 carbene. The TH 3 moves toward the base but only by a small amount in these dimers. However, when a Be 2+ or Mg 2+ dication is placed above the phenyl ring, the tetrel bond strength is greatly magnified reaching up to nearly 100 kcal mol −1 . This dication also induces a much higher degree of transfer which can be best categorized as half-transfer for the two N-bases and a near complete transfer for the carbene.
  5. F or c e d at a f or a fl a p pi n g f oil e n er g y h ar v e st er wit h a cti v e l e a di n g e d g e m oti o n o p er ati n g i n t h e l o w r e d u c e d fr e q u e n c y r a n g e i s c oll e ct e d t o d et er mi n e h o w l e a di n g e d g e m oti o n aff e ct s e n er g y h ar v e sti n g p erf or m a n c e. T h e f oil pi v ot s a b o ut t h e mi dc h or d a n d o p er at e s i n t h e l o w r e d u c e d fr e q u e n c y r a n g e of 𝑓𝑓more »𝑓𝑓 / 𝑈𝑈 ∞ = 0. 0 6 , 0. 0 8, a n d 0. 1 0 wit h 𝑅𝑅 𝑅𝑅 = 2 0 ,0 0 0 − 3 0 ,0 0 0 , wit h a pit c hi n g a m plit u d e of 𝜃𝜃 0 = 7 0 ∘ , a n d a h e a vi n g a m plit u d e of ℎ 0 = 0. 5 𝑓𝑓 . It i s f o u n d t h at l e a di n g e d g e m oti o n s t h at r e d u c e t h e eff e cti v e a n gl e of att a c k e arl y t h e str o k e w or k t o b ot h i n cr e a s e t h e lift f or c e s a s w ell a s s hift t h e p e a k lift f or c e l at er i n t h e fl a p pi n g str o k e. L e a di n g e d g e m oti o n s i n w hi c h t h e eff e cti v e a n gl e of att a c k i s i n cr e a s e d e arl y i n t h e str o k e s h o w d e cr e a s e d p erf or m a n c e. I n a d diti o n a di s cr et e v ort e x m o d el wit h v ort e x s h e d di n g at t h e l e a di n g e d g e i s i m pl e m e nt f or t h e m oti o n s st u di e d; it i s f o u n d t h at t h e m e c h a ni s m f or s h e d di n g at t h e l e a di n g e d g e i s n ot a d e q u at e f or t hi s p ar a m et er r a n g e a n d t h e m o d el c o n si st e ntl y o v er pr e di ct s t h e a er o d y n a mi c f or c e s.« less