A DFT study on 1,4-dihydro-1,4-azaborinine annulated linear polyacenes: Absorption spectra, singlet-triplet energy gap, aromaticity, and HOMO-LUMO energy modulation

2017 ◽  
Vol 38 (26) ◽  
pp. 2232-2240 ◽  
Author(s):  
Ramachandran Rakhi ◽  
Cherumuttathu H. Suresh
2015 ◽  
Vol 68 (9) ◽  
pp. 1438 ◽  
Author(s):  
Zahra Azizi ◽  
Mehdi Ghambarian ◽  
Mohammad A. Rezaei ◽  
Mohammad Ghashghaee

Various saturated five-membered N,X-heterocyclic carbenes (X = N, O, S, P, Si, C, and B) have been studied by ab initio and density functional theory (DFT) methods. The substitutions alter the properties of the reference carbene from the viewpoint of electronic structure, stability, nucleophilicity, and basicity. Our study shows that the oxygen containing carbene (X = O) induces the highest HOMO–LUMO energy gap (ΔEHOMO–LUMO), while carbene with X = N has the widest singlet–triplet energy difference (ΔEs–t). The nucleophilicity of the carbene derivatives increased upon replacement of C, Si, and B, with the effect of the boron substituent being more pronounced. In addition, the basicity of the structure increased for the carbene derivatives with X = C and B with the latter substitution imposing a remarkably higher effect. Moreover, the substitution of boron at the α-position of the carbene increased the nucleophilicity and basicity, while inducing a reduction in the values of ΔEs–t and ΔEHOMO–LUMO.


2016 ◽  
Vol 18 (35) ◽  
pp. 24631-24641 ◽  
Author(s):  
Ramachandran Rakhi ◽  
Cherumuttathu H. Suresh

Linear polyacene (LPA) mimics containing up to 34 rings have been designed by annulating dihydropyrazine units to LPA cores and they showed enhanced aromatic character than the LPA due to significant mixing of the N-lone pairs with the carbon π-orbitals.


2004 ◽  
Vol 140 (2-3) ◽  
pp. 127-133 ◽  
Author(s):  
Hafida Ammar Aouchiche ◽  
Sema Djennane ◽  
Abdou Boucekkine
Keyword(s):  

2011 ◽  
Vol 15 (11n12) ◽  
pp. 1220-1230 ◽  
Author(s):  
Al Mokhtar Lamsabhi ◽  
Manuel Yáñez ◽  
Otilia Mó ◽  
Cristina Trujillo ◽  
Fernando Blanco ◽  
...  

The UV-vis spectra of a series of subporphyrazines, SubPz(A,R), and subphthalocyanines, SubPc(A,R) ( A = F, Cl; R = H, F, CH3, C3H7, SCH3, SC2H5 and SPh), where A is the substituent attached to the central boron atom and R is the substituent attached to the periphery of the molecule have been analyzed through the use of TD–DFT calculations in vacuum and using chloroform as a solvent. The absorption spectra depend on both, the characteristics of the substituent attached to the periphery of the molecule and the extension of the π-system on going from SubPz to the SubPc analog. These latter effects lead to a red-shift of both the Q-band and the B-band, although the effect is larger for the former, mainly due to the increase of HOMO–LUMO energy gap on going from the SubPz to the SubPc analog. The effect of the substituents R is more intricate, because the profile of the absorption spectra changes depending on whether both substituents are on the same side (uu or dd) or on opposite sides (ud) of the molecular cone. Since the three conformers are rather close in energy, the observed spectra correspond, very likely, to the sum of the spectra of all of them.


2012 ◽  
Vol 11 (04) ◽  
pp. 723-734 ◽  
Author(s):  
SHAMOON AHMAD SIDDIQUI

Superhalogen properties of CoFn (n = 1 - 6) clusters have been investigated using density functional theory. These calculations reveal the unusual properties of a Cobalt (Co) atom interacting with fluorine (F) atoms. Up to six F atoms are bound to a single Co atom, which results in increase of electron affinities as successive fluorine atoms are attached, reaching a peak value of 7.43 eV for CoF5 . The large HOMO–LUMO energy gap, both in neutral and anionic form, further provide evidence of their stability. These unusual properties brought about by involvement of inner shell 3d-electrons, which not only allow CoFn (n = 1 - 6) clusters to belong to the class of superhalogens but also show that its valence can exceed the nominal value of 2 or 3.


Author(s):  
Jihyeon Kim ◽  
Heechan Kim ◽  
Sechan Lee ◽  
Giyun Kwon ◽  
Taewon Kang ◽  
...  

A new bipolar-type redox-active organic material with a wide HOMO–LUMO energy gap is designed though the ‘p–n fusion’ strategy.


2006 ◽  
Vol 05 (03) ◽  
pp. 595-608 ◽  
Author(s):  
KRIENGSAK SRIWICHITKAMOL ◽  
SONGWUT SURAMITR ◽  
POTJAMAN POOLMEE ◽  
SUPA HANNONGBUA

The structural and energetic properties of polyfluorene and its derivatives were investigated, using quantum chemical calculations. Conformational analysis of bifluorene was performed by using ab initio (HF/6-31G* and MP2/6-31G*) and density functional theory (B3LYP/6-31G*) calculations. The results showed that the local energy minimum of bifluorene lies between the coplanar and perpendicular conformation, and the B3LYP/6-31G* calculations led to the overestimation of the stability of the planar pi systems. The HOMO-LUMO energy differences of fluorene oligomers and its derivatives — 9,9-dihexylfluorene (DHPF), 9,9-dioctylfluorene (PFO), and bis(2-ethylhexyl)fluorene (BEHPF) — were calculated at the B3LYP/6-31G* level. Energy gaps and effective conjugation lengths of the corresponding polymers were obtained by extrapolating HOMO-LUMO energy differences and the lowest excitation energies to infinite chain length. The lowest excitation energies and the maximum absorption wavelength of polyfluorene were also performed, employing the time-dependent density functional theory (TDDFT) and ZINDO methods. The extrapolations, based on TDDFT and ZINDO calculations, agree well with experimental results. These theoretical methods can be useful for the design of new polymeric structures with a reducing energy gap.


2019 ◽  
Vol 75 (7) ◽  
pp. 1079-1083
Author(s):  
Tanwawan Duangthongyou ◽  
Ramida Rattanakam ◽  
Kittipong Chainok ◽  
Songwut Suramitr ◽  
Thawatchai Tuntulani ◽  
...  

The title compound, C31H30N2S2O6, possesses crystallographically imposed twofold symmetry with the two C atoms of the central benzene ring and the C atom of its methyl substituent lying on the twofold rotation axis. The two dansyl groups are twisted away from the plane of methylphenyl bridging unit in opposite directions. The three-dimensional arrangement in the crystal is mainly stabilized by weak hydrogen bonds between the sulfonyl oxygen atoms and the hydrogen atoms from the N-methyl groups. Stacking of the dansyl group is not observed. From the DFT calculations, the HOMO–LUMO energy gap was found to be 2.99 eV and indicates n→π* and π→π* transitions within the molecule.


2021 ◽  
Vol 4 (4) ◽  
pp. 236-251
Author(s):  
A. S. Gidado ◽  
L. S. Taura ◽  
A. Musa

Pyrene (C16H10) is an organic semiconductor which has wide applications in the field of organic electronics suitable for the development of organic light emitting diodes (OLED) and organic photovoltaic cells (OPV). In this work, Density Functional Theory (DFT) using Becke’s three and Lee Yang Parr (B3LYP) functional with basis set 6-311++G(d, p) implemented in Gaussian 03 package was  used to compute total energy, bond parameters, HOMO-LUMO energy gap, electron affinity, ionization potential, chemical reactivity descriptors, dipole moment, isotropic polarizability (α), anisotropy of polarizability ( Δ∝) total first order hyper-polarizability () and second order hyperpolarizability (). The molecules used are pyrene, 1-chloropyrene and 4-chloropyrene  in gas phase and in five different solvents: benzene, chloroform, acetone, DMSO and water. The results obtained show that solvents and chlorination actually influenced the properties of the molecules. The isolated pyrene in acetone has the largest value of HOMO-LUMO energy gap of and is a bit closer to a previously reported experimental value of  and hence is the most stable. Thus, the pyrene molecule has more kinetic stability and can be described as low reactive molecule. The calculated dipole moments are in the order of 4-chloropyrene (1.7645 D) < 1-chloropyrene (1.9663 D) in gas phase. The anisotropy of polarizability ( for pyrene and its derivatives were found to increase with increasing polarity of the solvents.  In a nutshell, the molecules will be promising for organic optoelectronic devices based on their computed properties as reported by this work.


2020 ◽  
Vol 86 (1) ◽  
pp. 770-781
Author(s):  
Akihiro Shimizu ◽  
Yu Ishizaki ◽  
Shun Horiuchi ◽  
Takashi Hirose ◽  
Kenji Matsuda ◽  
...  
Keyword(s):  

Sign in / Sign up

Export Citation Format

Share Document