Chiral Nonlinear Luminescence Study of Pentaoxonium Salt Molecules Driven by Internal Electric Field Induced by Orbital Polarization

doi:10.12422/j.issn.1006-396X.2025.01.009

Abstract

Abstract:

Based on density-functional theory (DFT) and wave function analysis procedures, the optical and molecular absorption properties of two structurally different pentacyclooxonium salt molecules have been investigated, and the physical mechanism of the formation of a built-in electric field due to orbital polarization caused by structural distortions, which induces charge transfer and leads to a nonlinear optical spectrum, has been explored.The properties result from the orbital polarization-induced built-in electric field driving charge transfer due to structural distortion. Theoretical analysis of ultraviolet-visible absorption spectroscopy (UV-vis) spectra is first performed to investigate the optical properties. The electronic excitation characteristics of the built-in electric field-driven charge transfer in molecules are analyzed in detail by transition density matrix (TDM) and charge differential density (CDD). Combining transition electric dipole moment density (TEDM) and transition magnetic dipole moment density (TMDM) analysis, the physical mechanism of the structure-induced chirality in their electronic circular dichroism (ECD) spectra is revealed. The results can provide theoretical references for the preparation of novel chiral materials as well as the research and development of optoelectronic materials and their practical applications.

Key words: Built-in electric field drive, Charge transfer, UV-vis, Electronic circular dichroism

摘要：

基于密度泛函理论（DFT）和波函数分析程序，研究了两种结构不同的五环氧鎓盐分子的光学吸收性质和分子吸收性质，并探讨了由结构扭曲导致轨道极化而形成内建电场，从而诱导电荷转移并导致非线性光谱的物理机制。通过紫外可见光吸收光谱（UV-vis）的理论分析，对两种五环氧鎓盐分子的光学特性进行了理论研究；利用跃迁密度矩阵（TDM）和电荷差分密度（CDD）图，详细探讨了分子内建电场驱动电荷转移的电子激发特性；结合跃迁电偶极矩密度（TEDM）与跃迁磁偶极矩密度（TMDM）的分析，揭示了其电子圆二色（ECD）光谱的结构诱导手性的物理机制。研究结果可为新型手性材料的制备以及光电材料的研发及实际应用提供理论参考。

关键词: 内建电场, 电荷转移, 紫外可见光吸收, 电子圆二色

CLC Number:

TQ591

Yue LI, Xinwen GAI, Bo ZHAO, Jingang WANG. Chiral Nonlinear Luminescence Study of Pentaoxonium Salt Molecules Driven by Internal Electric Field Induced by Orbital Polarization[J]. Journal of Petrochemical Universities, 2025, 38(1): 65-73.

李悦, 盖新雯, 赵波, 王金刚. 轨道极化诱导内建电场驱动五环氧鎓盐分子的手性非线性发光研究[J]. 石油化工高等学校学报, 2025, 38(1): 65-73.

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URL: https://journal.lnpu.edu.cn/syhg/EN/10.12422/j.issn.1006-396X.2025.01.009

https://journal.lnpu.edu.cn/syhg/EN/Y2025/V38/I1/65

Figures/Tables 7

Fig.1 Three-dimensional molecular structure diagrams of structure A and structure B

Fig.2 The UV-vis spectra and combined UV-vis spectra of structure A and structure B

Fig.3 The TDM and CDD diagram of Structure A

Fig.4 The TDM and CDD diagram of Structure B

Fig.5 The ECD spectra and combined ECD spectra of structure A and structure B

Fig.6 The transition electric dipole moment and transition magnetic dipole moment of S2 and S8 of structure A

Fig.7 The transition electric dipole moments and transition magnetic dipole moments of S3 and S8 of structure B

References 37

1	CHEN X， LU X J， BAN Y， et al. Electronic analogy of the goos-hänchen effect： A review［J］. Journal of Optics， 2013， 15（3）： 033001.
2	WANG Z J， CHENG F， WINSOR T， et al. Optical chiral metamaterials： A review of the fundamentals， fabrication methods and applications［J］. Nanotechnology， 2016， 27（41）： 412001.
3	MU X J， HU L， CHENG Y Q， et al. Chiral surface plasmon-enhanced chiral spectroscopy： Principles and applications［J］. Nanoscale， 2021， 13（2）： 581-601.
4	冯伟键，邹怡，王金刚. 凯库勒烯芳香性及光诱导电荷转移物理机制研究［J］. 石油化工高等学校学报， 2024， 37（2）： 24-30.
	FENG W J， ZOU Y， WANG J G. Aromaticity of kekulene and physical mechanism of photoinduced charge transfer［J］. Journal of Petrochemical Universities， 2024， 37（2）： 24-30.
5	闫荣，孙智广，高楠，等. 核壳结构中手性分子诱导的等离激元光学活性［J］. 辽宁石油化工大学学报， 2023， 43（5）： 20-28.
	YAN R， SUN Z G， GAO N， et al. Plasmon optical activity induced by chiral molecules in core-shell structures［J］. Journal of Liaoning Petrochemical University， 2023， 43（5）： 20-28.
6	GUO C Y， PUTZKE C， KONYZHEVA S， et al. Switchable chiral transport in charge-ordered kagome metal CsV₃Sb₅［J］. Nature， 2022， 611（7936）： 461-466.
7	SUN L C， CHEN Y C， SUN M T， et al. Physical mechanism of fluorescence and chirality of functionalized graphene quantum dots［J］. The Journal of Physical Chemistry C， 2022， 126（30）： 12845-12859.
8	陈璐鑫，卓绿燕， TCHAMENI A P，等. 温敏聚合物/纳米SiO₂复合材料的制备与性能评价［J］. 油田化学， 2023， 40（1）： 12-18.
	CHEN L X， ZHUO L Y， TCHAMENI A P， et al. Synthesis and solution properties of temperature-sensitive polymer/nano-SiO₂ composite N-AMPA［J］. Oilfield Chemistry， 2023， 40（1）： 12-18.
9	邓佳，张奇，王栋，等. 压力驱动条件下页岩微纳米孔隙CO₂/CH₄竞争吸附特性［J］. 东北石油大学学报， 2021， 45（5）： 109-116.
	DENG J， ZHANG Q， WANG D， et al. Competitive adsorption characteristics of CO₂/CH₄ in micro-nano pores by pressure-driven for shale reservoir［J］. Journal of Northeast Petroleum University， 2021， 45（5）： 109-116.
10	李盛龙，孙玮，吴晶，等. 纳米铁酸铋的制备、改性及光催化应用［J］. 石油炼制与化工， 2024， 55（2）： 135-143.
	LI S L， SUN W， WU J， et al. Fabrication， modification and photocatalytic applications of bismuth ferrite nanomaterials［J］. Petroleum Processing and Petrochemicals， 2024， 55（2）： 135-143.
11	刘聪，张钦库，高楠，等. Ba₄ln₂O₇光催化降解罗丹明 B 的影响因素［J］. 当代化工， 2021， 50（3）： 514-517.
	LIU C， ZHANG Q K， GAO N， et al. Influence factors of photocatalytic degradation of rhodamine B by Ba₄In₂O₇［J］. Contemporary Chemical Industry， 2021， 50（3）： 514-517.
12	李银成，林介本，梁俊辉，等. 无铅钙钛矿纳米晶的制备及其光催化二氧化碳还原性能研究［J］. 低碳化学与化工， 2024， 49（5）： 21-27.
	LI Y C， LIN J B， LIANG J H， et al. Study on preparation of lead-free perovskite nanocrystals and their photocatalytic performances in carbon dioxide reduction［J］. Low-Carbon Chemistry and Chemical Engineering， 2024， 49（5）： 21-27.
13	ZHU S Y， SUN M T. Electronic circular dichroism and raman optical activity： Principle and applications［J］. Applied Spectroscopy Reviews， 2021， 56（7）： 553-587.
14	SUN M T， ZHANG Z L， WANG P J， et al. Remotely excited Raman optical activity using chiral plasmon propagation in Ag nanowires［J］. Light： Science & Applications， 2013， 2（11）： e112.
15	潘永凯，陈运荣. 手性噁唑啉的不对称催化合成研究进展［J］. 辽宁石油化工大学学报， 2021， 41（4）： 9-16.
	PAN Y K， CHEN Y R. Advances in asymmetric catalytic synthesis of chiral oxazolines［J］. Journal of Liaoning Petrochemical University， 2021， 41（4）： 9-16.
16	何习楠，张晓楠，谢勋杰，等. 多维异质结光催化剂g-C₃N₄/WO₃的制备及应用［J］. 化工环保， 2024， 44（2）： 249-256.
	HE X N， ZHANG X N， XIE X J， et al. Preparation and application of multi-dimensional heterojunction photocatalyst g-C₃N₄/WO₃［J］. Environmental Protection of Chemical Industry， 2024， 44（2）： 249-256.
17	SAM CHAN H S， NGUYEN Q N N， PATON R S， et al. Synthesis， characterization，and reactivity of complex tricyclic oxonium ions， proposed intermediates in natural product biosynthesis［J］. Journal of the American Chemical Society， 2019， 141（40）： 15951-15962.
18	MEERWEIN H， HINZ G， HOFMANN P， et al. Über tertiäre oxoniumsalze， I［J］. Journal für Praktische Chemie， 1937， 147（10-12）： 257-285.
19	LAMBERT J B， JOHNSON D H. The stereochemistry and inversion of trivalent oxygen［J］. Journal of the American Chemical Society， 1968， 90（5）： 1349-1350.
20	BRADDOCK D C. A hypothesis concerning the biosynthesis of the obtusallene family of marine natural products via electrophilic bromination［J］. Organic Letters， 2006， 8（26）： 6055-6058.
21	BARTON D H R， NAKANISHI K， METH-COHN O， et al. Comprehensive natural products chemistry［M］. Amsterdam： Elsevier， 1999.
22	KIKUCHI H， SUZUKI T， KUROSAWA E， et al. The structure of notoryne，a halogenated C15 nonterpenoid with a novel carbon skeleton from the red alga Laurenda nipponica yamada［J］. Bulletin of the Chemical Society of Japan， 1991， 64（6）： 1763-1775.
23	BONNEY K J， BRADDOCK D C. A unifying stereochemical analysis for the formation of halogenated C15-acetogenin medium-ring ethers from Laurencia species via intramolecular bromonium ion assisted epoxide ring-opening and experimental corroboration with a model epoxide［J］. The Journal of Organic Chemistry， 2012， 77（21）： 9574-9584.
24	KIM B， LEE M， LEE M J， et al. Biomimetic asymmetric total synthesis of（-）-laurefucin via an organoselenium-mediated intramolecular hydroxyetherification［J］. Journal of the American Chemical Society， 2008， 130（49）： 16807-16811.
25	ZHANG Y A， YAW N， SNYDER S A. General synthetic approach for the laurencia family of natural products empowered by a potentially biomimetic ring expansion［J］. Journal of the American Chemical Society， 2019， 141（19）： 7776-7788.
26	SMITH O， POPESCU M V， HINDSON M J， et al. Control of stereogenic oxygen in a helically chiral oxonium ion［J］. Nature， 2023， 615（7952）： 430-435.
27	MU X J， CHEN X T， WANG J G， et al. Visualizations of electric and magnetic interactions in electronic circular dichroism and raman optical activity［J］. The Journal of Physical Chemistry. A， 2019， 123（37）： 8071-8081.
28	KOHN W， SHAM L J. Self-consistent equations including exchange and correlation effects［J］. Physical Review， 1965， 140（4A）： A1133-A1138.
29	FRISCH M J， TRUCKS G W， SCHLEGEL H B， et al. Gaussian 16 Revision A.03［CP］. Wallingford： Gaussian Inc.， 2016.
30	LU T， CHEN F W. Multiwfn： A multifunctional wavefunction analyzer［J］. Journal of Computational Chemistry， 2012， 33（5）： 580-592.
31	MU X J， CAI K， WEI W J， et al. Dependence of UV-visible absorption characteristics on the migration distance and the hyperconjugation effect of a methine chain［J］. The Journal of Physical Chemistry C， 2018， 122（14）： 7831-7837.
32	MU X J， WANG J G， SUN M T. Visualization of photoinduced charge transfer and electron-hole coherence in two-photon absorption［J］. The Journal of Physical Chemistry C， 2019， 123（23）： 14132-14143.
33	SUN M T， CHEN J N， XU H X. Visualizations of transition dipoles， charge transfer， and electron-hole coherence on electronic state transitions between excited states for two-photon absorption［J］. The Journal of Chemical Physics， 2008， 128（6）： 064106.
34	LIU Z Y， LU T， CHEN Q X. An sp-hybridized all-carboatomic ring， cyclo［18］carbon： Electronic structure， electronic spectrum， and optical nonlinearity［J］. Carbon， 2020， 165： 461-467.
35	SUN M T. Control of structure and photophysical properties by protonation and subsequent intramolecular hydrogen bonding［J］. The Journal of Chemical Physics， 2006， 124（5）： 054903.
36	MU X， SUN M. The linear and non-linear optical absorption and asymmetrical electromagnetic interaction in chiral twisted bilayer graphene with hybrid edges［J］. Materials Today Physics， 2020， 14： 100222.
37	HUMPHREY W， DALKE A， SCHULTEN K. VMD： Visual molecular dynamics［J］. Journal of Molecular Graphics， 1996， 14（1）： 33-38.