NDLI: Ferrocene/fullerene hybrids showing large second-order nonlinear optical activities: impact of the cage unit size

Content Provider	World Health Organization (WHO)-Global Index Medicus
Author	Ma, Na-na Zhu, Chang-li Qiu, Yong-qing Wang, Li Wang, Wen-yong
Description	Author Affiliation: Wang WY ( Institute of Functional Material Chemistry, Faculty of Chemistry, Northeast Normal University, Changchun 130024, Jilin, People's Republic of China. qiuyq466@nenu.edu.cn.)
Abstract	The electron donor–acceptor complexes, which undergo intramolecular charge transfer under external stimulus, are an emerging class of materials showing important application in nonlinear optics. Synthesizing ferrocene/fullerene complexes through face-to-face fusion would enjoy the merits of both ferrocene and fullerene due to their strong donor–acceptor interactions. Four ferrocene/fullerene hybrid complexes with the gradual extension of fullerene cage size, including $CpFe(C_{60}H_{5}),$ $CpFe(C_{66}H_{5}),$ $CpFe(C_{70}H_{5}),$ and $CpFe(C_{80}H_{5})$ (Cp is cyclopentadienyl), have been investigated by density functional theory. These hybrid molecules give eclipsed and staggered isomers. The main reason that the eclipsed isomer is stable is that the eclipsed structure possesses large CpFe⋯fullerene bonding energy. The CpFe⋯fullerene interaction is smaller than that of Cp⋯Fefullerene, which must come from two different interfaces. The presence of covalent bond character between CpFe and fullerene is supported by the localized orbital locator, deformation of electron density distribution and energy decomposition analysis. Significantly, the absorption bands and first hyperpolarizabilities of these hybrid complexes are strongly sensitive to the fullerene cage size, which is ascribed to a change in the charge transfer pattern, especially for $CpFe(C_{80}H_{5}),$ which displays reverse π → π* charge transfer from bottom to top cage, leading to notable hyperpolarizability. Investigation of the structure–property relationship at the molecular level can benefit the design and preparation of such hybrid complexes in chemistry and materials science.
ISSN	14779226
Issue Number	21
Journal	Dalton Trans.
Volume Number	44
e-ISSN	13645447
Language	English
Publisher	Royal Society of Chemistry
Publisher Date	2015-06-07
Publisher Place	Great Britain (UK)
Access Restriction	Subscribed
Subject Keyword	Ferrous Compounds Chemistry Fullerenes Models, Chemical Optical Rotation Journal Article Research Support, Non-U.S. Gov't
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

Sl.	Authority	Responsibilities	Communication Details
1	Ministry of Education (GoI), Department of Higher Education	Sanctioning Authority	https://www.education.gov.in/ict-initiatives
2	Indian Institute of Technology Kharagpur	Host Institute of the Project: The host institute of the project is responsible for providing infrastructure support and hosting the project	https://www.iitkgp.ac.in
3	National Digital Library of India Office, Indian Institute of Technology Kharagpur	The administrative and infrastructural headquarters of the project	Dr. B. Sutradhar bsutra@ndl.gov.in
4	Project PI / Joint PI	Principal Investigator and Joint Principal Investigators of the project	Dr. B. Sutradhar bsutra@ndl.gov.in Prof. Saswat Chakrabarti will be added soon
5	Website/Portal (Helpdesk)	Queries regarding NDLI and its services	support@ndl.gov.in
6	Contents and Copyright Issues	Queries related to content curation and copyright issues	content@ndl.gov.in
7	National Digital Library of India Club (NDLI Club)	Queries related to NDLI Club formation, support, user awareness program, seminar/symposium, collaboration, social media, promotion, and outreach	clubsupport@ndl.gov.in
8	Digital Preservation Centre (DPC)	Assistance with digitizing and archiving copyright-free printed books	dpc@ndl.gov.in
9	IDR Setup or Support	Queries related to establishment and support of Institutional Digital Repository (IDR) and IDR workshops	idr@ndl.gov.in