Gas phase molecular complexes. Multiple charge-transfer bands in the spectra of alkyl halide-iodine atom systems

1976 ◽  
Vol 98 (18) ◽  
pp. 5460-5464 ◽  
Author(s):  
Robert L. Strong ◽  
Jack A. Kaye
Keyword(s):  
Charge Transfer ◽  
Gas Phase ◽  
Iodine Atom ◽  
Alkyl Halide ◽  
Molecular Complexes ◽  
Multiple Charge

Photoelectron Spectroscopy and Molecular Complexes Having Multiple Charge Transfer Bands

1972 ◽  
Vol 27 (7) ◽  
pp. 1165-1166 ◽  
Author(s):  
S Pignataro ◽  
G Aloisi
Keyword(s):  
Charge Transfer ◽  
Spectral Data ◽  
Photoelectron Spectroscopy ◽  
Ultra Violet ◽  
Molecular Complexes ◽  
Energy Spectra ◽  
Energy Separation ◽  
Photoelectron Energy ◽  
Multiple Charge ◽  
Vacant Orbital

AbstractThe ultra violet spectral data for molecular complexes showing multiple charge-transfer bands are compared with the photoelectron energy spectra of the free donors.The energy separation between the first two photoelectron bands of the free donor is shown to correspond to the energy separation between the absorption maxima of the charge-trans­fer band for a number of complexes involving aromatic com­pounds as donors.This indicates that in the cases considered the multiple charge-transfer maxima are due to transitions from two diffe­rent occupied orbitals of the donor to the same vacant orbital of the acceptor

Symmetric resonance multiple charge transfer of Neq+and Arq+(q⩽4)

1981 ◽  
Vol 14 (5) ◽  
pp. 881-891 ◽  
Author(s):  
Y Kaneko ◽  
T Iwai ◽  
S Ohtani ◽  
K Okuno ◽  
N Kobayashi ◽  
...  
Keyword(s):  
Charge Transfer ◽  
Multiple Charge ◽  
Symmetric Resonance

Charge Transfer Molecular Complexes of 4-(Dimethylamino)pyridine with Some Conventional and Unconventional Acceptors Involving Fluoroarenes

2006 ◽  
Vol 71 (9) ◽  
pp. 1359-1370 ◽  
Author(s):  
Usama M. Rabie
Keyword(s):  
Charge Transfer ◽  
Nmr Spectra ◽  
Molecular Complexes ◽  
Outer Sphere ◽  
Formation Constants ◽  
Stoichiometric Ratio ◽  
Spectral Bands ◽  
Elemental Analyses ◽  
Ct Complexes ◽  
Solid Complexes

Charge transfer (CT) complexes of 4-(dimethylamino)pyridine (DMAP) with iodine as a typical σ-type acceptor and with typical π-type acceptor, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ), have been synthesized and characterized. Octafluorotoluene (OFT), octafluoronaphthalene (OFN), perfluorophenanthrene (PFP), and 2,3,5,6-tetrafluoropyridine-4-carbonitrile (TFP) were also used as acceptors for interaction with DMAP. Properties of such CT complexes were investigated by UV/VIS and IR spectra, and elemental analyses of the isolated complexes. The systems DMAP-iodine and DMAP-DDQ are characterized by formation of triiodide ions (I3-) and DDQ•- anion radicals, respectively, which is proposed to occur via initial formation of outer-sphere CT complexes. The systems (DMAP-OFT, DMAP-OFN, DMAP-PFP and DMAP-TFP) are characterized by the appearance of new UV/VIS spectral bands assigned as CT bands; they also furnished the corresponding solid complexes with the stoichiometric ratio 1:1. 1H and 19F NMR spectra were used on confirming the formation of the DMAP-PFP CT complexes. The formation constants (KCT) and molar absorption coefficients (εCT) of the latter complex were obtained.

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>

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