Vibrational spectroscopic evidence of unconventional hydrogen bonds

Fujii, Asuka; Patwari, G. Naresh; Ebata, Takayuki; Mikami, Naohiko

doi:10.1016/s1387-3806(02)00774-1

Cited by 53 publications

(52 citation statements)

References 77 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…upon the formation of dihydrogen (37). Other than in those compounds, we have observed that the N-H stretching frequency of lithium amidoborane is blue shifted relative to its parent compound (Fig.…”

Section: −δmentioning

confidence: 72%

“…when the dihydrogen bonding forms (37). Likewise, the N-H stretching in the complex between 2-pyridone (as the proton donor) and borane-trimethylamine also shows a red shift by 5 cm…”

Section: −δmentioning

confidence: 93%

“…The absence of the dihydrogen bonding not only alters the structure stabilizing factor of LiNH 2 BH 3 , it may also cause significant change in the dehydrogenation mechanism of this complex. In principle, the attractive interaction between the dihydrogen bonded atoms strongly lowers the activation energy for hydrogen release of ammonia borane (37,54,55) and also some potential complexes for hydrogen storage (53). Although there is no dihydrogen bond, LiNH 2 BH 3 dehydrogenates at lower temperature than ammonia borane, which refers to a different dehydrogenation mechanism other than mere H δ+ .…”

Section: −δmentioning

confidence: 99%

See 2 more Smart Citations

High-pressure study of lithium amidoborane using Raman spectroscopy and insight into dihydrogen bonding absence

Najiba

Chen

2012

Proc. Natl. Acad. Sci. U.S.A.

View full text Add to dashboard Cite

One of the major obstacles to the use of hydrogen as an energy carrier is the lack of proper hydrogen storage material. Lithium amidoborane has attracted significant attention as hydrogen storage material. It releases ∼10.9 wt% hydrogen, which is beyond the Department of Energy target, at remarkably low temperature (∼90°C) without borazine emission. It is essential to study the bonding behavior of this potential material to improve its dehydrogenation behavior further and also to make rehydrogenation possible. We have studied the high-pressure behavior of lithium amidoborane in a diamond anvil cell using in situ Raman spectroscopy. We have discovered that there is no dihydrogen bonding in this material, as the N-H stretching modes do not show redshift with pressure. The absence of the dihydrogen bonding in this material is an interesting phenomenon, as the dihydrogen bonding is the dominant bonding feature in its parent compound ammonia borane. This observation may provide guidance to the improvement of the hydrogen storage properties of this potential material and to design new material for hydrogen storage application. Also two phase transitions were found at high pressure at 3.9 and 12.7 GPa, which are characterized by sequential changes of Raman modes.H ydrogen economy has been considered as potentially efficient and environmental friendly alternative energy solution (1). However, one of the most important scientific and technical challenges facing the "hydrogen economy" is the development of safe and economically viable on-board hydrogen storage for fuel cell applications, especially to the transportation sector. Ammonia borane (BH 3 NH 3 ), a solid state hydrogen storage material, possesses exceptionally high hydrogen content (19.6 wt%) and in particular, it contains a unique combination of protonic and hydridic hydrogen, and on this basis, offers new opportunities for developing a practical source for generating molecular dihydrogen (2-5). Stepwise release of H 2 takes place through thermolysis of ammonia borane, yielding one-third of its total hydrogen content (6.5 wt%) in each heating step, along with emission of toxic borazine (6-8). Recently, research interests are focusing on how to improve discharge of H 2 from ammonia borane, including lowering the dehydrogenation temperature and enhancing hydrogen release rate using different techniques, e.g., nanoscaffolds (9), ionic liquids (10), acid catalysis (11), base metal catalyst (12), or transition metal catalysts (13, 14). More recently, significant attention is given to chemical modification of ammonia borane through substitution of one of the protonic hydrogen atoms with an alkali or alkaline-earth element (15-21). Lithium amidoborane (LiNH 2 BH 3 ) has been successfully synthesized by ball milling LiH with NH 3 BH 3 (15-18). One of the driving forces suggested for the formation of LiNH 2 BH 3 is the chemical potential of the protonic H δ+ in NH 3 and the hydridic H δ− in alkali metal hydrides making them tend to combine, producing H 2 + LiNH 2 BH 3 ....

show abstract

Section: −δmentioning

confidence: 72%

“…when the dihydrogen bonding forms (37). Likewise, the N-H stretching in the complex between 2-pyridone (as the proton donor) and borane-trimethylamine also shows a red shift by 5 cm…”

Section: −δmentioning

confidence: 93%

Section: −δmentioning

confidence: 99%

See 1 more Smart Citation

High-pressure study of lithium amidoborane using Raman spectroscopy and insight into dihydrogen bonding absence

Najiba

Chen

2012

Proc. Natl. Acad. Sci. U.S.A.

View full text Add to dashboard Cite

show abstract

“…The infrared spectra of bare molecules and molecular clusters in their electronic ground state can be recorded using the IR-UV double-resonance spectroscopic technique. [43][44][45][46] Figure 2 depicts the technique for both the fluorescence and the ion detection. In this technique, a UV pulse is tuned to resonance between the zeroth vibrational level of the ground state (S 0 ; v'' = 0) and the zeroth vibrational level of the excited state (S 1 ; v' = 0).…”

Section: Methodsmentioning

confidence: 99%

Phenylacetylene: A Hydrogen Bonding Chameleon

et al. 2010

View full text Add to dashboard Cite

Molecules with multiple hydrogen bonding sites offer the opportunity to investigate competitive hydrogen bonding. Such an investigation can become quite interesting, particularly when the molecule of interest has neither lone-pair electrons nor strongly acidic/basic groups. Phenylacetylene is one such molecule with three hydrogen bonding sites that cannot be ranked into any known hierarchical pattern. Herein we review the structures of several binary complexes of phenylacetylene investigated using infrared optical double-resonance spectroscopy in combination with high-level ab initio methods. The diversity of intermolecular structures formed by phenylacetylene with various reagents is remarkable. The nature of intermolecular interaction with various reagents is the result of a subtle balance between various configurations and competition between the electrostatic and dispersion energy terms, while trying to maximize the total interaction strength.

show abstract

“…Other interactions may play significant roles, namely: CAHÁÁÁO unconventional H-bonds between a benzene H of one monomer and the O atom of an OH of the other monomer [12][13][14][15][16][17]; OHÁÁÁp unconventional H-bonds between the H of the OH of one monomer and the p-system of the other monomer [18][19][20]; HÁÁÁp interactions between a benzene H of one monomer and the p-system of the other monomer [21][22][23][24][25][26]; and p…p interactions between the p systems of the two rings, when the rings are facing each other [27][28][29].…”

mentioning

confidence: 99%

A comparative study of the dimers of selected hydroxybenzenes

Kabanda

Mammino

2011

Int J of Quantum Chemistry

View full text Add to dashboard Cite

Hydroxybenzenes are the parent compounds of large classes of derivatives, many of which exhibit biological activities. This work presents the results of a comparative study of the dimers of selected hydroxybenzenes, considering all the possible mutual geometrical arrangements of the two monomers and comparing their relative stabilities and interaction energies. The OHÁÁÁOH hydrogen bond between the two monomers is the dominant stabilizing factor, with frequent preference for mutual perpendicularity of the two aromatic rings. CAHÁÁÁO unconventional H-bonds, OHÁÁÁp unconventional H-bonds, HÁÁÁp interactions and pÁÁp interactions also may play significant roles. The factors stabilizing individual hydroxybenzenes (presence of intramolecular hydrogen bonds; number, positioning and orientation of the OH groups; symmetry features) have greater influence on the dimers' relative energy than on the interaction energy between monomers. While results from different calculations methods (HF, MP2, and DFT/B3LYP) show consistency for all the features just-mentioned, they show some relevant differences in the way they take into account different types of interactions between monomers, resulting in some differences in the geometry arrangements of the monomers in the lowest energy dimers and in differences in the relative preferences among higher-energy dimer geometries.

show abstract

Vibrational spectroscopic evidence of unconventional hydrogen bonds

Cited by 53 publications

References 77 publications

High-pressure study of lithium amidoborane using Raman spectroscopy and insight into dihydrogen bonding absence

High-pressure study of lithium amidoborane using Raman spectroscopy and insight into dihydrogen bonding absence

Phenylacetylene: A Hydrogen Bonding Chameleon

A comparative study of the dimers of selected hydroxybenzenes

Contact Info

Product

Resources

About