{"title":"关于(N^C^N)Pt(II)Cl 复合物二阶非线性特性周围效应的理论研究","authors":"Huiying Wang, Feiwu Chen","doi":"10.1016/j.saa.2024.125338","DOIUrl":null,"url":null,"abstract":"<div><div>Pt(II) complexes are widely used as nonlinear optical (NLO) materials. The geometric and electronic structures, second-order NLO property and UV–Vis absorption spectra of (N^C^N)Pt(II)Cl complexes (<strong>1</strong>–<strong>4</strong>) N^C^N binding by central benzene and two lateral N-heterocycles) are evaluated by density functional theory (DFT) and time-dependent DFT calculations. The detailed environmental effect of total first hyperpolarizability (<em>β</em><sub>tot</sub>) in the solution and crystal phases is simulated by polarized continuum model (PCM) and quantum mechanics/molecular mechanics (QM/MM) method, respectively. The results highlight that the complex <strong>3</strong> exhibits largest <em>β</em><sub>tot</sub> value in the gas, solution and crystal phases which can be attributed to the higher electron π-delocalization of ligands. Further, an evident red shift towards longer wavelength is observed for the complex <strong>3</strong>. The origin of larger <em>β</em><sub>tot</sub> value can be reasonably interpreted by the two-level model. In addition, the surrounding exerts an important influence on modulating second-order NLO properties. The solvent effect results in the larger <em>β</em><sub>tot</sub> value than that of gas phase. The intermolecular interaction plays an important role in crystal phase. The formation of dimer can reduce the <em>β</em><sub>tot</sub> value in comparison with the <em>β</em><sub>tot</sub> value of the monomer in the crystal phase, because the centrosymmetric configuration of dimer implies a decrease of dipole moment (<em>μ</em>) in contrast to the large <em>μ</em> value of monomer. It is expected that this work will provide some guidance for designing Pt(II) NLO materials.</div></div>","PeriodicalId":433,"journal":{"name":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","volume":null,"pages":null},"PeriodicalIF":4.3000,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Theoretical investigation on the surrounding effects of second-order nonlinear properties for (N^C^N)Pt(II)Cl complexes\",\"authors\":\"Huiying Wang, Feiwu Chen\",\"doi\":\"10.1016/j.saa.2024.125338\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Pt(II) complexes are widely used as nonlinear optical (NLO) materials. The geometric and electronic structures, second-order NLO property and UV–Vis absorption spectra of (N^C^N)Pt(II)Cl complexes (<strong>1</strong>–<strong>4</strong>) N^C^N binding by central benzene and two lateral N-heterocycles) are evaluated by density functional theory (DFT) and time-dependent DFT calculations. The detailed environmental effect of total first hyperpolarizability (<em>β</em><sub>tot</sub>) in the solution and crystal phases is simulated by polarized continuum model (PCM) and quantum mechanics/molecular mechanics (QM/MM) method, respectively. The results highlight that the complex <strong>3</strong> exhibits largest <em>β</em><sub>tot</sub> value in the gas, solution and crystal phases which can be attributed to the higher electron π-delocalization of ligands. Further, an evident red shift towards longer wavelength is observed for the complex <strong>3</strong>. The origin of larger <em>β</em><sub>tot</sub> value can be reasonably interpreted by the two-level model. In addition, the surrounding exerts an important influence on modulating second-order NLO properties. The solvent effect results in the larger <em>β</em><sub>tot</sub> value than that of gas phase. The intermolecular interaction plays an important role in crystal phase. The formation of dimer can reduce the <em>β</em><sub>tot</sub> value in comparison with the <em>β</em><sub>tot</sub> value of the monomer in the crystal phase, because the centrosymmetric configuration of dimer implies a decrease of dipole moment (<em>μ</em>) in contrast to the large <em>μ</em> value of monomer. It is expected that this work will provide some guidance for designing Pt(II) NLO materials.</div></div>\",\"PeriodicalId\":433,\"journal\":{\"name\":\"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":4.3000,\"publicationDate\":\"2024-10-28\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S138614252401504X\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"SPECTROSCOPY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S138614252401504X","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"SPECTROSCOPY","Score":null,"Total":0}
Theoretical investigation on the surrounding effects of second-order nonlinear properties for (N^C^N)Pt(II)Cl complexes
Pt(II) complexes are widely used as nonlinear optical (NLO) materials. The geometric and electronic structures, second-order NLO property and UV–Vis absorption spectra of (N^C^N)Pt(II)Cl complexes (1–4) N^C^N binding by central benzene and two lateral N-heterocycles) are evaluated by density functional theory (DFT) and time-dependent DFT calculations. The detailed environmental effect of total first hyperpolarizability (βtot) in the solution and crystal phases is simulated by polarized continuum model (PCM) and quantum mechanics/molecular mechanics (QM/MM) method, respectively. The results highlight that the complex 3 exhibits largest βtot value in the gas, solution and crystal phases which can be attributed to the higher electron π-delocalization of ligands. Further, an evident red shift towards longer wavelength is observed for the complex 3. The origin of larger βtot value can be reasonably interpreted by the two-level model. In addition, the surrounding exerts an important influence on modulating second-order NLO properties. The solvent effect results in the larger βtot value than that of gas phase. The intermolecular interaction plays an important role in crystal phase. The formation of dimer can reduce the βtot value in comparison with the βtot value of the monomer in the crystal phase, because the centrosymmetric configuration of dimer implies a decrease of dipole moment (μ) in contrast to the large μ value of monomer. It is expected that this work will provide some guidance for designing Pt(II) NLO materials.
期刊介绍:
Spectrochimica Acta, Part A: Molecular and Biomolecular Spectroscopy (SAA) is an interdisciplinary journal which spans from basic to applied aspects of optical spectroscopy in chemistry, medicine, biology, and materials science.
The journal publishes original scientific papers that feature high-quality spectroscopic data and analysis. From the broad range of optical spectroscopies, the emphasis is on electronic, vibrational or rotational spectra of molecules, rather than on spectroscopy based on magnetic moments.
Criteria for publication in SAA are novelty, uniqueness, and outstanding quality. Routine applications of spectroscopic techniques and computational methods are not appropriate.
Topics of particular interest of Spectrochimica Acta Part A include, but are not limited to:
Spectroscopy and dynamics of bioanalytical, biomedical, environmental, and atmospheric sciences,
Novel experimental techniques or instrumentation for molecular spectroscopy,
Novel theoretical and computational methods,
Novel applications in photochemistry and photobiology,
Novel interpretational approaches as well as advances in data analysis based on electronic or vibrational spectroscopy.