First observation of a dihydrogen bond involving the Si–H group in phenol-diethylmethylsilane clusters by infrared-ultraviolet double-resonance spectroscopy

Abstract

We have experimentally identified a dihydrogen bond involving the Si-H group in phenol-diethylmethylsilane (DEMS) clusters for the first time by IR-UV double-resonance spectroscopy. Vibrational shifts to lower frequency of 21-29 cm(-1) were found for the OH stretching vibration of three isomers of the phenol-DEMS clusters. Spectral simulations based on the MP2 calculations also support our observation. In addition to these clusters, dihydrogen bonds were also observed in the phenol-H(2)O-DEMS and (phenol)(2)-DEMS clusters, which exhibited much stronger interactions than the phenol-DEMS clusters.

Vibrational population relaxation of hydrogen-bonded phenol complexes in solution: Investigation by ultrafast infrared pump–probe spectroscopy

“…Hydrogen-bonded complexes of phenol with various bases in non-polar solvents have been intensively studied by steady-state IR spectroscopy over many decades [1,[21][22][23][24]. Furthermore, the electronic and vibrational states of phenol clusters solvated by small molecules have been intensively studied in the gas phase [25][26][27][28][29][30]. By using various bases to act as hydrogen-bond acceptors, we can change the strength of the hydrogen bonds in the complex and thus investigate in detail the influence of hydrogen bonding on vibrational dynamics.…”

Time‐dependent density functional theory study on excited‐state dihydrogen bonding OH···HGe of the dihydrogen‐bonded phenol‐triethylgermanium complex

“…The redshifts of the vibrational modes that are associated with dihydrogen bond provide very useful information on the dihydrogen bonding ability. The magnitude of OÀ ÀH redshift of the phenol-TEGH complex (83 cm 21 ) is comparable to that of the phenol-DEMS complex (94 cm 21 ), 37 but significantly smaller than that of the phenol-BTMA complex (202 cm 21 ). 36 It infers that dihydrogen bonding of borane-amines complex is much stronger than those of the relative silanes and germanes.…”

“…Upon electronic excitation, the GeÀ ÀH and OÀ ÀH vibrational modes downshift to 1882 cm 21 ). It can be speculated that the intermolecular dihydrogen bonding of germanes strengthens more than that of silanes in the S 1 state.…”

“…[15][16][17][18][19][20] Thus, dihydrogen bond can be viewed as a precursor to dehydrogenation reactions. 21,22 In addition, dihydrogen bond also has potential application in crystal engineering and catalysis. [23][24][25][26][27] In the late 1960s, Brown and coworkers recognized this interaction as a true hydrogen bond for the first time.…”

“…Ishikawa et al have detected intermolecular dihydro-gen bond containing silicon of the phenol-diethylmethylsilane (DEMS) complex in the gas phase. 21 Recently, Singh et al reported the first observation of intermolecular dihydrogen bond OÀ ÀHÁÁÁHÀ ÀGe of the phenol-triethylgermanium (TEGH) complex. 22 To investigate the dihydrogen-bonded complex between phenol and TEGH hydride, laser-induced fluorescence excitation (LIF), fluorescence-detected infrared (FDIR), and IR-UV holeburning spectroscopic studies were employed in supersonic jet.…”