Donor–acceptor complexes of Lewis bases with bromine monochloride in the gas phase. Some generalisations from rotational spectroscopy

1995 ◽  
Vol 91 (12) ◽  
pp. 1881-1883 ◽  
Author(s):  
A. C. Legon
Keyword(s):  
Gas Phase ◽  
Rotational Spectroscopy ◽  
Lewis Bases ◽  
Donor Acceptor

scholarly journals Tuning of Hyperpolarizability, One- and Two-Photon Absorption of D-A and D-A-A Type Intramolecular Charge Transfer Based Sensors

2019 ◽  
Author(s):  
Pralok K. Samanta ◽  
Md Mehboob Alam ◽  
Ramprasad Misra ◽  
Swapan K. Pati
Keyword(s):  
Charge Transfer ◽  
Gas Phase ◽  
Density Functional ◽  
Intramolecular Charge Transfer ◽  
Photon Absorption ◽  
First Hyperpolarizability ◽  
Two Photon Absorption ◽  
Two Photon ◽  
Nlo Response ◽  
Donor Acceptor

Solvents play an important role in shaping the intramolecular charge transfer (ICT) properties of π-conjugated molecules, which in turn can affect their one-photon absorption (OPA) and two-photon absorption (TPA) as well as the static (hyper)polarizabilities. Here, we study the effect of solvent and donor-acceptor arrangement on linear and nonlinear optical (NLO) response properties of two novel ICT-based fluorescent sensors, one consisting of hemicyanine and dimethylaniline as electron withdrawing and donating groups (molecule 1), respectively and its boron-dipyrromethene (BODIPY, molecule 2)-fused counterpart (molecule 3). Density functional theoretical (DFT) calculations using long-range corrected CAM-B3LYP and M06-2X functionals, suitable for studying properties of ICT molecules, are employed to calculate the desired properties. The dipole moment (µ) as well as the total first hyperpolarizability (β<sub>total</sub>) of the studied molecules in the gas phase is dominantly dictated by the component in the direction of charge transfer. The ratios of vector component of first hyperpolarizability (β<sub>vec</sub>) to β<sub>total</sub> also reveal unidirectional charge transfer process. The properties of the medium significantly affect the OPA, hyperpolarizability and TPA properties of the studied molecules. Time dependent DFT (TDDFT) calculations suggest interchanging between two lowest excited states of molecule 3 from the gas phase to salvation. The direction of charge polarization and dominant transitions among molecular orbitals involved in the OPA and TPA processes are studied. The results presented are expected to be useful in tuning the NLO response of many ICT-based chromophores, especially those with BODIPY acceptors.<br>

Metallocenylborane, IV. Diborylverbindungen des Ferrocens und Cymantrens.

1976 ◽  
Vol 31 (8) ◽  
pp. 1028-1034 ◽  
Author(s):  
Werner Ruf ◽  
Thomas Renk ◽  
Walter Siebert
Keyword(s):  
Redox Reaction ◽  
Lewis Acidity ◽  
Lewis Bases ◽  
Nmr Data ◽  
Halogen Exchange ◽  
Donor Acceptor ◽  
C Nmr

Ferrocene reacts with BI3 and BBr3 to give 1,1′-bis(dihalogenboryl)ferrocenes; the cyclopentadienylring in cymantrene is twice borylated by BI3. By halogen exchange with AsF3 and AsCl3, by methylation with Sn(CH3)4, by cleavage of (C2H5)2O, by redox reaction with (CH3S)2 and by reaction with (C2H5)2NH the corresponding diborylferrocenes are obtained. The air-sensitive halogenborylferrocenes form donor-acceptor compounds with Lewis bases. 1H, 11B and 13C NMR data reflect increasing π-acceptor properties with increasing Lewis acidity of the boryl groups.

scholarly journals Elucidating the multiple structures of pipecolic acid by rotational spectroscopy

2019 ◽  
Vol 21 (8) ◽  
pp. 4155-4161 ◽  
Author(s):  
A. Simão ◽  
C. Cabezas ◽  
I. León ◽  
E. R. Alonso ◽  
S. Mata ◽  
...  
Keyword(s):  
Amino Acid ◽  
Gas Phase ◽  
Theoretical Data ◽  
Pipecolic Acid ◽  
Conformational Space ◽  
Rotational Spectroscopy ◽  
Multiple Structures ◽  
First Time

The complex conformational space of the non-proteinogenic cyclic amino acid pipecolic acid has been explored in the gas phase for the first time, with 9 conformers characterized via a combination of CP-FTMW and LA-FTMW techniques, supported by theoretical data.

Trifluoromethylated Compounds with SiNN and SiON Backbone, and the Crystal Structures of Trimethyl- and Trichloro(trifluoromethyl)silane

2009 ◽  
Vol 64 (1) ◽  
pp. 83-92 ◽  
Author(s):  
Markus Woski ◽  
Norbert W. Mitzel
Keyword(s):  
Gas Phase ◽  
Solution Nmr ◽  
X Ray Diffraction ◽  
Experimental Ir ◽  
In Situ Techniques ◽  
Quantum Chemical Methods ◽  
Conformational Preferences ◽  
Donor Acceptor ◽  
Solid State Structures

The reaction of (F3C)Cl2SiCl3 with the lithiated hydrazine LiN(Me)NMe2 gives the compound (F3C)Cl2SiN(Me)NMe2 (1) and in traces Cl3SiN(Me)NMe2 (2). The reactions with LiN(SiMe3)NMe2 and LiONMe2 give (F3C)Cl2SiN(SiMe3)NMe2 (4) and (F3C)Cl2SiONMe2 (5), respectively. The compounds were characterised by multinuclear solution NMR, gas-phase IR spectroscopy and mass spectrometry. Information about conformational preferences of 1 and 4 can be extracted by comparing experimental IR spectra with those calculated by quantum chemical methods (B3LYP/6-311G**). The former show the gas phase of the β -donor-acceptor silanes 1 and 4 to be dominated by the anti conformations, while the calculations show a preference for the gauche conformers. The crystal structure of Cl3SiN(Me)NMe2 (2) has been determined. The solid-state structures of the Ruppert reagent F3C-SiMe3 (1) and its chlorine analogue F3C-SiCl3 (2) have also been determined by X-ray diffraction of single crystals grown by in situ techniques.

scholarly journals Non covalent interactions stabilizing the chiral dimer of CH2ClF: a rotational study

2019 ◽  
Vol 21 (7) ◽  
pp. 3695-3700 ◽  
Author(s):  
Laura B. Favero ◽  
Assimo Maris ◽  
Sonia Melandri ◽  
Paolo Ottaviani ◽  
Walther Caminati
Keyword(s):  
Spectral Analysis ◽  
Gas Phase ◽  
Rotational Spectroscopy ◽  
Non Covalent Interactions ◽  
Covalent Interactions

Two C–H⋯Cl–C and one C–H⋯F–C bonds stabilize (by 5.9 kJ mol−1) the dimer of chlorofluoromethane observed by rotational spectroscopy in the gas phase. The spectral analysis is complicated by the quadrupolar effects of the two nonequivalent Cl nuclei.

scholarly journals Gas phase complexes of H3N⋯CuF and H3N⋯CuI studied by rotational spectroscopy and ab initio calculations: the effect of X (X = F, Cl, Br, I) in OC⋯CuX and H3N⋯CuX

2016 ◽  
Vol 18 (19) ◽  
pp. 13638-13645 ◽  
Author(s):  
Dror M. Bittner ◽  
Susanna L. Stephens ◽  
Daniel P. Zaleski ◽  
David P. Tew ◽  
Nicholas R. Walker ◽  
...  
Keyword(s):  
Ab Initio Calculations ◽  
Ab Initio ◽  
Gas Phase ◽  
Microwave Spectroscopy ◽  
Rotational Spectroscopy

Complexes of H3N⋯CuF and H3N⋯CuI have been synthesised in the gas phase and characterized by microwave spectroscopy.

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