NLO potential exploration for D–π–A heterocyclic organic compounds by incorporation of various π-linkers and acceptor units

Khalid, Muhammad; Khan, Muhammad Usman; Shafiq, Iqra; Hussain, Riaz; Mahmood, Khalid; Hussain, Ajaz; Jawaria, Rifat; Hussain, Amjad; Imran, Muhammad; Assiri, Mohammed A.; Ali, Akbar; Rehman, Muhammad Fayyaz ur; Sun, Keyu; Li, Yuzhen

doi:10.1016/j.arabjc.2021.103295

Cited by 92 publications

(68 citation statements)

References 48 publications

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“… 37 The value of electronegativity of a molecule is defined as the chemical potential, which is determined using the expression μ = ( E HOMO + E LUMO )/2. 23b , 38 There is a direct relation between hardness (η), energy gaps, stability of a compound, and chemical potential (μ), whereas in the case of reactivity, this relationship is inversed. 34b The calculated results of GRPs are tabulated in Table 3 .…”

Section: Results and Discussionmentioning

confidence: 99%

Influence of End-Capped Modifications in the Nonlinear Optical Amplitude of Nonfullerene-Based Chromophores with a D−π–A Architecture: A DFT/TDDFT Study

et al. 2022

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Nonlinear optical (NLO) materials have several uses in many fields such as solid physics, biology, medicine, nuclear physics, and material research. Therefore, a series of nonfullerene-based derivatives ( CC10D1 – CC10D8 ) with a D−π–A configuration was planned for the NLO investigation using CC10R as the reference molecule with structural alternations at acceptor moieties. Natural bonding orbital (NBO), UV–vis spectra, frontier molecular orbitals (FMOs), global reactivity parameters (GRPs), transition density matrix (TDM), and density of states (DOS) were analyzed using the M06/6-311G(d,p) functional in chloroform solvent to understand the NLO responses of CC10R and CC10D1 – CC10D8 . The highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) band gaps of CC10D1 – CC10D6 were illustrated to be lower than that of CC10R , with the larger bathochromic shift (726.408–782.674 nm) resulting in a significant NLO response. Along with the band gap, the FMO method also identified an efficient interfacial charge transfer from D to A moieties via a π-bridge, which was further supported by the DOS and TDM map. Moreover, NBO calculations demonstrated that extended hyperconjugation and strong internal molecular interactions were important in their stabilization. The dipole moment (μ), linear polarizability ⟨α⟩, hyperpolarizability (β total ), and second-order hyperpolarizability (γ total. ) were studied for CC10R and CC10D1 – CC10D8 . Among all of the derivatives, CC10D2 was proven to be the most appropriate candidate because of its suitable NLO behavior such as being well-supported by a reduced band gap (2.093 eV) and having a suitable maximum absorption wavelength (782.674 nm). Therefore, CC10D2 was reported to have a greater value of first hyperpolarizability (208 659.330 a.u.) compared with other derivatives and CC10R . For the second hyperpolarizability, a greater value was obtained for CC10R (5.855 × 10 7 a.u.), and its derivatives showed results comparable to that of the parent chromophore for γ total . This theoretical framework reveals that structural customization with different acceptor units plays a significant role in obtaining attractive NLO materials for optoelectronic applications.

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Section: Results and Discussionmentioning

confidence: 99%

Influence of End-Capped Modifications in the Nonlinear Optical Amplitude of Nonfullerene-Based Chromophores with a D−π–A Architecture: A DFT/TDDFT Study

et al. 2022

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“… 6 − 11 The main focus of researchers is to discover the crucial factors that can cause a tremendous increase in first and higher order hyperpolarizability values. 12 − 16 Previous studies have proved that along with first-order hyperpolarizabilities, second- and the third-order hyperpolarizabilities are also equally important properties of the NLO materials. 17 − 19 …”

Section: Introductionmentioning

confidence: 99%

Deciphering the Role of Alkali Metals (Li, Na, K) Doping for Triggering Nonlinear Optical (NLO) Properties of T-Graphene Quantum Dots: Toward the Development of Giant NLO Response Materials

et al. 2022

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Nanoscale nonlinear optical (NLO) materials have received huge attention of the scientists in current decades because of their enormous applications in optics, electronics, and telecommunication. Different studies have been conducted to tune the nonlinear optical response of the nanomaterials. However, the role of alkali metal (Li, Na, K) doping on triggering the nonlinear optical response of nanomaterials by converting their centrosymmetric configuration into noncentrosymmetric configuration is rarely studied. Therefore, to find a novel of way of making NLO materials, we have employed density functional theory (DFT) calculations, which helped us to explore the effect of alkali metal (Li, Na, K) doping on the nonlinear optical response of tetragonal graphene quantum dots (TGQDs). Ten new complexes of alkali metal doped TGQDs are designed theoretically. The binding energy calculations revealed the stability of alkali metal doped TGQDs. The NLO responses of newly designed complexes are evaluated by their polarizability, first hyperpolarizability (β o ), and frequency dependent hyperpolarizabilities. The Li@r8a exhibited the highest first hyperpolarizability (β o ) value of 5.19 × 10 5 au. All these complexes exhibited complete transparency in the UV region. The exceptionally high values of β o of M@TGQDs are accredited to the generation of diffuse excess electrons, as indicated by NBO analysis and PDOS. NCI analysis is accomplished to examine the nature of bonding interactions among alkali metal atoms and TGQDs. Our results suggest alkali metal doped TGQD complexes as potential candidates for nanoscale NLO materials with sufficient stability and enhanced NLO response. This study will open new doors for making giant NLO response materials for modern hi-tech applications.

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“…The most efficient and versatile strategies for the modulation of organic NLO properties have been widely used: redox switching perturbations, protonation/deprotonation, extended p conjugation, modifying push-pull donor (D) or acceptor (A) groups, doping metal atoms and so on. [12][13][14][15] Compared to pure organic NLO materials, transition metal complexes offer additional functionalities due to their charge transfer optical absorption bands involving d orbitals, resulting in the low-energy region of UV-Vis spectra which are related to large NLO responses. 16 Additionally, the often huge first hyperpolarizability (b) value of the metal complex is generally associated with metal-toligand charge transfer (MLCT), ligand-to-metal charge transfer (LMCT) and intraligand charge transfer (ILCT).…”

Section: Introductionmentioning

confidence: 99%

Theoretical investigation of electronic structures, second-order NLO responses of cyclometalated Ir(iii) and Rh(iii) counterpart complexes: effect of metal centers

Wang

Qiu

et al. 2022

New J. Chem.

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NLO potential exploration for D–π–A heterocyclic organic compounds by incorporation of various π-linkers and acceptor units

Cited by 92 publications

References 48 publications

Influence of End-Capped Modifications in the Nonlinear Optical Amplitude of Nonfullerene-Based Chromophores with a D−π–A Architecture: A DFT/TDDFT Study

Influence of End-Capped Modifications in the Nonlinear Optical Amplitude of Nonfullerene-Based Chromophores with a D−π–A Architecture: A DFT/TDDFT Study

Deciphering the Role of Alkali Metals (Li, Na, K) Doping for Triggering Nonlinear Optical (NLO) Properties of T-Graphene Quantum Dots: Toward the Development of Giant NLO Response Materials

Theoretical investigation of electronic structures, second-order NLO responses of cyclometalated Ir(iii) and Rh(iii) counterpart complexes: effect of metal centers

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