Phosphates branching effect on the structure, linear and NLO properties of linear phosphazenes

Hadji, Djebar

doi:10.1016/j.matchemphys.2021.124280

Cited by 22 publications

(3 citation statements)

References 81 publications

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“…A similar behavior is observed for polaronic state (Th*), where the minimum energy gap is seen for 9Th* (4.00 eV) with the maximum hyperpolarizability value of 2.7 × 10 4 au (see Figure ). The similar observation (inverse relation) is reported in some recent papers. − However, in certain cases, a direct relationship between hyperpolarizability and energy gap is also obtained. − …”

Section: Resultssupporting

confidence: 85%

Enhancement in Nonlinear Optical Response of Oligothiophenes by Induction of Polarons

Ejaz

Sarfaraz

Ayub

2023

ACS Appl. Electron. Mater.

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In this study, the electronic and nonlinear optical properties of neutral ((nTh) and polaronic states (nTh*) of oligothiophenes are studied. Electronic properties are evaluated through HOMO−LUMO gap, ionization potential (IP), and electronic affinity (EA). The results of global reactivity descriptors also indicate the stability of nTh*. The linear and nonlinear optical properties are evaluated through the polarizability and static and dynamic hyperpolarizabilities. The polaronic states of these polymers show high hyperpolarizability (β o ) up to 2.7 × 10 4 au as compared to neutral counterparts. This remarkable increase is mainly due to low transition energies arising from the induction of polaron. The NLO response of polaron-based oligothiophenes are much better than their neutral counterparts. Furthermore, the frequency dependent calculations for polaronic state of oligothiophenes (nTh*) are also performed at commonly used laser frequencies of 532 and 1064 nm. The results of frequency dependent calculations reveal that the values of dynamic hyperpolarizability are more pronounced than static hyperpolarizability. Time-dependent calculations show enough transparency of polaronic state of nTh* in the UV region, which reveals that the materials show good NLO response and could be used in the field of optoelectronics.

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Section: Resultssupporting

confidence: 85%

Enhancement in Nonlinear Optical Response of Oligothiophenes by Induction of Polarons

Ejaz

Sarfaraz

Ayub

2023

ACS Appl. Electron. Mater.

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“…Excellent agreement has been obtained in earlier studies. [48][49][50] Compared to PBE0, CAM-B3LYP, ωB97X-D, and M05-2X functionals; the B3LYP/6-311++G(d,p) level was found to give the best match with the experimental ∆𝜀 at 2.72 eV. This experimental ∆𝜀 value is measured by UV-vis (Fig.…”

Section: Frontier Molecular Orbitals (Fmos) Analysismentioning

confidence: 88%

Synthesis and characterization of novel thiosemicarbazide for nonlinear optical applications: combined experimental and theoretical study

HADJI,

BENMOHAMMED,

MOUCHAAL

et al. 2023

Rev.Roum.Chim.

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(E)-4-(4-methoxyphenyl)-1-((E)-3(2nitrophenyl) allylidene) thiosemicarbazide was synthesised and screened for nonlinear optical properties. The novel compound has been characterized by infrared spectroscopy, 1H and 13C nuclear magnetic resonance. The experimental and theoretical optical gap energy is obtained using the Tauc method and density functional theory and has been estimated to be around 2.72 and 2.69 eV, respectively. The synthesized thiosemicarbazide exhibits efficiency hyper-Rayleigh scattering hyperpolarizability is calculated to be 6794.51 a.u. at the PBE0 functional. A direct relationship of the hyper-Rayleigh scattering hyperpolarizability with the optical band gap and between the hyper-Rayleigh scattering hyperpolarizability and electric field-induced second harmonic generation is found. The study showed the potential of the novel thiosemicarbazide as nonlinear optical candidates.

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“…One method of preparing the parent polymer, [PCl 2 N] n , is through a melt ring-opening polymerization (ROP) of [PCl 2 N] 3 . Subsequently, replacing the chlorine atoms with various (R) substituents, the functionalized derivatives become versatile and find wide applications in diverse fields, including elastomers, fire-resistant materials, optical materials, − protective coatings, conductors, , interpenetrating polymer networks, nanofibers, catalysts, lubricants, and biomedical materials. ,, Researchers have extensively examined this reaction and alternative reactions involving Cl 3 PNSiMe 3 through experimentation in an attempt to comprehend its underlying mechanism. − However, despite their efforts, the intricacies of the chlorophosphazene ROP reaction remain inadequately understood.…”

Section: Introductionmentioning

confidence: 99%

Comprehensive Mechanistic Analysis of the Ring-Opening Polymerization of [PCl₂N]₃ Using Quantum Mechanical Calculations

Xue,

Salmon,

Ramlo

et al. 2024

Macromolecules

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The most popular method to synthesize polychlorophosphazenes, the parent of a prominent class of inorganic polymers, is the ring-opening polymerization (ROP) of [PCl 2 N] 3 . In contrast to the accepted (S N 1-initiated) ROP mechanism that begins with heterolytic P−Cl bond cleavage in [PCl 2 N] 3 , our quantum mechanical (QM) calculations suggest that the ROP can proceed through a S N 2-like route in which one [PCl 2 N] 3 can be attacked by a neighboring [PCl 2 N] 3 and hence transform through a four-center transition state (4C PNPCl TS), yielding a cyclic chlorophosphazene with a linear tail, termed a "tadpole". Meanwhile, two [PCl 2 N] 3 molecules can morph into [PCl 2 N] 6 (RR expansion) through a different four-center transition state (4C PNPN TS) without the assistance of a bridging chlorine. As the activation energy of these processes follows the trend tadpole backbite < chain branching < ROP initiation ≤ RR initiation = RR expansion < chain propagation (all within 241.2 ± 16 kJ/mol), the ROP and RR mechanisms compete toward product formation. Not only does our pioneering QM calculations unveil the pivotal role of the bridging chlorine in the S N 2 mechanism, it also explains its effect on reactivity of [PCl 2 N] 3 species, underscoring the significance of halogen substituents in modulating polymerization. By comprehensively examining the ROP, RR, linear propagation, and ring closure processes, we attempt to resolve long-standing queries in chlorophosphazene research, elucidating the wide variability in reaction pot products and the necessity of halogen substituents in specific processes. Thus, this work characterizes a variety of four-center transition states for the first time and introduces a novel mechanistic process for polymerization. Finally, our work provides an explanation of the existence of the chlorinated tadpole.

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Phosphates branching effect on the structure, linear and NLO properties of linear phosphazenes

Cited by 22 publications

References 81 publications

Enhancement in Nonlinear Optical Response of Oligothiophenes by Induction of Polarons

Enhancement in Nonlinear Optical Response of Oligothiophenes by Induction of Polarons

Synthesis and characterization of novel thiosemicarbazide for nonlinear optical applications: combined experimental and theoretical study

Comprehensive Mechanistic Analysis of the Ring-Opening Polymerization of [PCl₂N]₃ Using Quantum Mechanical Calculations

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Phosphates branching effect on the structure, linear and NLO properties of linear phosphazenes

Cited by 22 publications

References 81 publications

Enhancement in Nonlinear Optical Response of Oligothiophenes by Induction of Polarons

Enhancement in Nonlinear Optical Response of Oligothiophenes by Induction of Polarons

Synthesis and characterization of novel thiosemicarbazide for nonlinear optical applications: combined experimental and theoretical study

Comprehensive Mechanistic Analysis of the Ring-Opening Polymerization of [PCl2N]3 Using Quantum Mechanical Calculations

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Comprehensive Mechanistic Analysis of the Ring-Opening Polymerization of [PCl₂N]₃ Using Quantum Mechanical Calculations