{"title":"Exploring Spectral and Electrochemical Behavior of Hydroxy-N-Benzylideneanilines by Integrated Theoretical and Experimental Approaches","authors":"Prabhudatta Hota, Supriya Priyambada Biswal, Manas Ranjan Dash, Bijnyan Ranjan Das, Pramila Kumari Misra","doi":"10.1002/poc.4659","DOIUrl":"https://doi.org/10.1002/poc.4659","url":null,"abstract":"<div>\u0000 \u0000 <p>The present work explored the effect of –OH group substitution (o/p) on the spectral and electrochemical behavior of N-benzylideneaniline. The geometry optimization of unsubstituted and (o/p)-OH-substituted analogs revealed the coplanarity of the molecules. The vibrational spectra of the compounds were computed using density functional theory (DFT) and compared with the experimental data. The observed bands were assigned based on total energy distribution (TED). Predicted electronic absorption spectra from time-dependent density functional theory (TD-DFT) calculation were compared with the UV–visible spectra of the molecules. The analysis of the lowest spin-allowed (singlet-singlet) excited states divulged possible electronic transition. The o-substituted benzylideneaniline possessed the lowest highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) energy gap among the substituted and unsubstituted analogs. The intramolecular contacts were interpreted using natural bond orbital and localized molecular orbital analysis. The –CH=N– linkage was investigated as a bridge for the electron delocalization from the donor to acceptor moieties. The manifestation of a reduction peak in the cyclic voltammetric studies confirmed the electrochemical behavior in the –OH-substituted molecule, which was diffusion-controlled. The discrepancy in the electrochemical property concerning the position of the –OH substituent of the candidate molecules was put forward.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 12","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642381","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Muzammil Hussain, Muhammad Adnan, Zobia Irshad, Riaz Hussain, Hany W. Darwish, Jongchul Lim
{"title":"Correlating Chemical Structure and Charge Carrier Dynamics in Phenanthrocarbazole-Based Hole Transporting Materials for Efficient Perovskite Solar Cells","authors":"Muzammil Hussain, Muhammad Adnan, Zobia Irshad, Riaz Hussain, Hany W. Darwish, Jongchul Lim","doi":"10.1002/poc.4662","DOIUrl":"https://doi.org/10.1002/poc.4662","url":null,"abstract":"<div>\u0000 \u0000 <p>Polymeric hole transport materials (HTMs) have emerged because of their potential to produce dopant-free, efficient, and stable perovskite solar cells (PSCs). Therefore, we engineered 10 novel donor materials (SMH1–SMH10) containing phenanthrocarbazole-based polymeric structures for organic and PSCs. These molecules underwent bridging-core modifications using different spacers, such as furan (N1), pyrrole (N2), benzene (N3), pyrazine (N4), dioxane (N5), isoxazole (N6), isoindole (N7), indolizine (N8), double bond (N9), and pyrimidine (N10), in comparison to reference molecule R. The study examined the structure–property relationship and the impact of these modifications on the optical, photovoltaic, photophysical, and optoelectronic characteristics of the newly designed SMH1–SMH10 series. Density functional theory (DFT) and time-dependent density functional theory (TD-DFT) calculations were conducted to analyze frontier molecular orbitals, density of states, reorganization energies, open-circuit voltage, transition density matrix, and charge transfer processes. Results show that the newly designed molecules (SMH1–SMH10) exhibited superior optoelectronics characteristics compared to the R molecule. Among these, SMH4 is the most promising candidate, with a small band gap (2.79 eV), low electron and hole mobility (<i>λ</i><sub>e</sub> 0.0028 eV, <i>λ</i><sub>h</sub> 0.0020 eV), lower binding energy (<i>E</i><sub>b</sub> 0.58 eV), high <i>λ</i><sub>max</sub> values (656.42 nm in gas, 573.34 nm in chlorobenzene), and a high <i>V</i><sub>oc</sub> of 1.30 V. Therefore, this study demonstrated that bridging-core modifications offer a simple and effective strategy for designing desirable characteristics molecules for photovoltaic applications.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 12","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642405","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"A Theoretical Perspective on the Stereochemistry of Benzoanellated Aroyl-X,N-Ketene Acetal Derivatives","authors":"Francisco A. Martins, Matheus P. Freitas","doi":"10.1002/poc.4658","DOIUrl":"https://doi.org/10.1002/poc.4658","url":null,"abstract":"<div>\u0000 \u0000 <p>Ketene 1,3-oxazoles and their derivatives present intriguing structures for the study of rotational barriers due to their pseudo–double-bond character stemming from resonance in the ketene moiety. A diverse range of compounds featuring this motif underwent quantum-chemical investigation to elucidate the nature of the stereochemical singularity observed in numerous cases. Because rotational barriers in most instances are too high to permit rapid interconversion, the findings are ascribed to thermodynamic rather than kinetic factors in the gas phase and within an implicit polar medium. The stabilities are attributed to internal hydrogen bonding where feasible. However, in cases where this is not possible, chalcogen bonding rather than steric effects governs the stereochemical preferences, particularly when S and Se comprise the heterocycle of these compounds. These findings hold promise for guiding the design of compounds whose properties hinge on stereochemistry and resonant structures, such as dyes.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 12","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-09-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142642030","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Enhanced Hyperpolarizabilities Through p-Phenylene Bridges: Computational Studies on Metamerism and Functional Molecular Properties of Pyridinium–Dicyanomethanide-Based Zwitterions","authors":"Sanyasi Sitha","doi":"10.1002/poc.4657","DOIUrl":"10.1002/poc.4657","url":null,"abstract":"<p>Para-phenylene-bridged pyridinium (acceptor)–dicyanomethanide (donor)-based zwitterions were computationally investigated and are reported here. Reichardt's metamer was found to be twisted and Brooker's metamer in near-planar conformation. Natural bond orbital (NBO) analysis showed that mesomeric resonance is helping Brooker's metamer but found to be not helpful for Reichardt's metamer. To assess the impacts of metamerism and aromatic bridges, fundamental molecular properties like dipole moments (μ), polarizabilities (<i>α</i>), hyperpolarizabilities (<i>β</i>), and adiabatic absorptions of these two molecules were analyzed and then directly compared with their counterpart zwitterions without any bridges (<i>previously reported</i>). Results of impact of metamerism: Reichardt's metamer showed around <i>three times enhanced</i> hyperpolarizabilities (ωB97xD: <i>β</i> = 1577.1 × 10<sup>−30</sup> esu) than the Brooker's metamer (ωB97xD: <i>β</i> = 532.5 × 10<sup>−30</sup> esu). Impacts of <i>p</i>-phenylene bridges: Compared to their respective D–A directly connected zwitterions reported previously (in ωB97xD methodology, Reichardt's: <i>β</i> = 257.2 × 10<sup>−30</sup> esu and Brooker's: <i>β</i> = 67.2 × 10<sup>−30</sup> esu), respective <i>p</i>-phenylene-bridged zwitterions showed <i>five to eight times enhanced</i> hyperpolarizabilities. This report highlights the better efficiencies of Reichardt's metamer over Brooker's metamer and aromatically bridged over the directly connected zwitterions. Current findings may be helpful in the designing of efficient functional molecular chromophores, and aromatic bridge combined with zwitterions can be solutions to nonlinear transparency trade-off problem.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 12","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.4657","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142191271","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Darón I. Freedberg, Nicholas V. Hud, Max Kopelevich, Daniel J. O'Leary, Jane Strouse
{"title":"In Memoriam: The Life and Scientific Accomplishments of Frank A. L. Anet (1926–2024)","authors":"Darón I. Freedberg, Nicholas V. Hud, Max Kopelevich, Daniel J. O'Leary, Jane Strouse","doi":"10.1002/poc.4656","DOIUrl":"10.1002/poc.4656","url":null,"abstract":"<p>A memorial tribute detailing the life and scientific accomplishments of Frank A. L. Anet, a pioneer of nuclear magnetic resonance (NMR) spectroscopy who discovered bedrock principles in organic chemistry and magnetic resonance. He was the first to show that nuclear Overhauser effects could provide structural information, significantly impacting future NMR applications. In the 1960s and 1970s, he built entire multinuclear NMR spectrometers operating as high as 396 MHz for protons, detecting nuclei inaccessible to commercial instruments, and operating at very low temperatures for studying molecular structure and dynamics. A titan of physical organic chemistry, Frank made important contributions in the areas of conformational analysis, stereochemistry, isotope effects, NMR relaxation theory, and chemical origins of life.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 12","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-08-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/poc.4656","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142191272","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Michelle T. Custodio Castro, Carlos O. Della Védova, Rosana M. Romano
{"title":"Exploring Conformational Preferences in XC(W)ZY Molecules With X, Y = F, Cl, Br and W, Z = O, S, Se: Unraveling the Influence of Conjugative and Anomeric Interactions","authors":"Michelle T. Custodio Castro, Carlos O. Della Védova, Rosana M. Romano","doi":"10.1002/poc.4654","DOIUrl":"10.1002/poc.4654","url":null,"abstract":"<div>\u0000 \u0000 <p>The relative stabilities of the <i>syn</i>- and <i>anti</i>-conformers of 72 molecules belonging to the XC(W)ZY type, with X, Y = F, Cl, Br and W, Z = O, S, Se, have been computed using the B3LYP/aug-cc-pVDZ approximation. The conformational preferences, represented by the energy differences between the two rotamers, exhibit a systematic trend in relation to both the halogen atoms and the chalcogen atoms. These computational predictions are in agreement with available experimental results. The NBO formalism was employed to assess the influence of both the conjugative and anomeric interactions on the relative energy of the conformers. It has been determined that the conjugative interaction provides a satisfactory explanation for the energy differences between rotamers. In contrast, the anomeric interactions favors the <i>syn</i>-conformation in all cases. The relative stabilities between XC(W)ZY/YC(W)ZX and XC(W)ZY/XC(Z)WY constitutional isomers have also been computed and correlated with the experimental data.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 11","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142191280","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Novel Trifunctional Intramolecular Frustrated Lewis Pair Derived From Aminoboronic Acid for Converting CO2 Into Valuable Chemicals","authors":"Mohmmad Faizan, Guntupalli Santhosh, Madhumita Chakraborty, Ravinder Pawar","doi":"10.1002/poc.4655","DOIUrl":"10.1002/poc.4655","url":null,"abstract":"<div>\u0000 \u0000 <p>The conversion of CO<sub>2</sub> into valuable chemicals remains a significant challenge for achieving environmental sustainability, primarily due to the stability of the CO<sub>2</sub> molecule. This necessitates the development of efficient and ecofriendly catalysts. In recent years, frustrated Lewis pairs (FLPs) have shown promise for CO<sub>2</sub> utilization. In this study, we introduce α-aminodiboronic acid (DBA), a novel trifunctional aminoboronic acid, as an intramolecular FLP for converting CO<sub>2</sub> into cyclic carbonate and formic acid. Using density functional theory (DFT) calculations, we explored the reaction mechanism and investigated DBA's electronic structure through molecular electrostatic potential surface (MESP) and natural bond orbital (NBO) analyses. Our results reveal that one −B (OH)<sub>2</sub> group induces an unusual state of frustration in the molecule due to charge transfer from the nitrogen atom's lone pair to the π* orbitals, enhancing catalytic performance. The additional −B (OH)<sub>2</sub> group serves as an anchoring site for reactive species. The epoxide activation energy is reduced by approximately 27 kcal/mol compared to the uncatalyzed reaction, and the reduction of CO<sub>2</sub> occurs with a requirement of 26 kcal/mol. The additional −B (OH)<sub>2</sub> plays a crucial role in the catalytic mechanism and minimizes the energies of various structures observed in the reaction path. The reaction energetics align with structural analysis observations, marking this study as the first report on single-molecule trifunctional FLPs for transforming CO<sub>2</sub> into valuable chemicals.</p>\u0000 </div>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 11","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142191319","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Theoretical investigations on N2H5N5/PDO cocrystal via a first-principles study","authors":"Zhipeng Chen, Junqi Wang, Qingshan Xie, Chen Yang, Changlin Zhou","doi":"10.1002/poc.4653","DOIUrl":"10.1002/poc.4653","url":null,"abstract":"<p>The exploration of <i>cyclo</i>-N<sub>5</sub>ˉ-based energetic cocrystals represents a noteworthy avenue within pentazolate chemistry, focusing on leveraging cocrystallization to enhance stability. Recently, a novel cocrystal explosive, N<sub>2</sub>H<sub>5</sub>N<sub>5</sub>/PDO, was developed by combining N<sub>2</sub>H<sub>5</sub>N<sub>5</sub> with pyrazine 1,4-dioxide (PDO), exhibiting promising detonation characteristics and reduced sensitivity. This study endeavors to elucidate how the structure and noncovalent interactions impact the performance of N<sub>2</sub>H<sub>5</sub>N<sub>5</sub>/PDO through a first-principles investigation. The results indicate that the enhanced hydrogen bonding and wave-like crystal packing structure within the cocrystal effectively bolster its stability compared to N<sub>2</sub>H<sub>5</sub>N<sub>5</sub>. The N···H and O···H interactions, in conjunction with π–π interactions, emerge as critical elements driving cocrystal formation. Compared to the pure N<sub>2</sub>H<sub>5</sub>N<sub>5</sub>, the detonation performance of the cocrystal exhibits a slight decline, albeit with a noticeable reduction in sensitivity.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 11","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-08-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142191320","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Torsional influences on cross‐conjugated thieno[3,4‐b]thiophene photochromes","authors":"Nicholas P. Adams, John D. Tovar","doi":"10.1002/poc.4650","DOIUrl":"https://doi.org/10.1002/poc.4650","url":null,"abstract":"Photoresponsive conjugated polymers are a promising target for modern organic electronics. Numerous photoswitchable repeat units have been included covalently within polymeric structures to enable responsive chromic materials, most commonly through side‐chain appendages or through formal conjugation along a π‐conjugated backbone. We recently disclosed a new design whereby the photoswitch elements are cross conjugated to a conjugated polymer main chain. In this case, we found that the extent of photoconversion was dictated in part by competitive main chain light absorption, which could be suppressed by using a photoswitching motif that carried most of the frontier molecular orbital densities. Here, we report the modeling and synthesis of a series of thieno[3,4‐<jats:italic>b</jats:italic>]thiophene (TT)‐based photochromes with various aromatic flankers imparting varying degrees of steric bulk and π‐conjugation in order to elucidate the balancing act between steric and electronic factors to promote photochromism. These model systems provide a better understanding of the behavior of photochromic units within extended oligomeric and polymeric π‐conjugated materials.","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"8 1","pages":""},"PeriodicalIF":1.8,"publicationDate":"2024-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141883605","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Theoretical study of atomic electronegativity effects on the excited-state behavior of fluorescent compounds of citrinin","authors":"Yue Gao, Meiheng Lv, Zexu Cai, Yuhang Zhang, Tingting Wang, Jianyong Liu, Fangjian Shang, Wenze Li","doi":"10.1002/poc.4651","DOIUrl":"10.1002/poc.4651","url":null,"abstract":"<p>The present work focuses on the light-induced behavior of citrinin derivatives in relation to atomic electronegativity. A detailed theoretical study on the photophysical properties and excited-state behavior of fluorescent compounds of citrinin (Cit-O, Cit-S, and Cit-Se, with different atomic electronegativity) has been conducted, and the effect of electronegativity on the proton transfer in this system has been explained. First, the relevant hydrogen bond parameters and infrared vibrational spectra of the optimized geometrical configurations have been insightfully investigated. It is elucidated that the hydrogen bond is strengthened after photoexcitation, and it provides a driving force for excited-state intramolecular proton transfer (ESIPT). In addition, the frontier molecular orbitals were analyzed, and the intramolecular charge transfer process in all Cit systems, the phenomenon of charge redistribution, facilitates the ESIPT reaction. By constructing potential energy surfaces for different transfer paths, the atomic electronegativity impact on the ESIPT dynamical behavior of the Cit system was determined. This work clarifies the mechanism of the intramolecular proton transfer process in the excited state of citrinin molecules and complements the theoretical study of the atomic electronegativity-regulated citrinin system, which provides a corresponding theoretical basis for the design and synthesis of new luminescence-adjustable citrinin systems.</p>","PeriodicalId":16829,"journal":{"name":"Journal of Physical Organic Chemistry","volume":"37 11","pages":""},"PeriodicalIF":1.9,"publicationDate":"2024-07-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"141774711","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}