| Prediction of robustly large molecular second-order nonlinear optical properties of terpyridine-substituted hexamolybdates: structural modelling towards a rational entry to NLO materials. | |
| | |
MedLine Citation:
|
PMID: 20188613 Owner: NLM Status: MEDLINE |
Abstract/OtherAbstract:
|
We have explored an innovative, versatile, and novel molecular hybrid containing polyoxometalate (POM) cluster linked with terpyridine ligand via pi-bridged donor-acceptor (D-A) configuration. The dipole polarizabilities, density of states, and second-order nonlinear optical (NLO) properties of terpyridine-substituted hexamolybdates have been investigated by using time-dependent density functional response theory (TDDFT). This class of organic-inorganic hybrid compounds possesses a robustly large molecular second-order NLO response, especially [Mo(6)O(18)(N(4)C(25)H(16)I(2))](2-) (system 5) and [Mo(6)O(17)(N(4)C(25)H(16)(CN)(2))(N(4)C(25)H(16)(CN)(2))](2-) (system 10) with the static second-order polarizability (beta(vec)) computed to be 1209.25x10(-30)esu and 1622.67x10(-30)esu respectively. Thus, these systems have the possibility to be excellent second-order nonlinear optical materials. Analysis of the major contributions to the beta(vec) value suggests that the charge transfer (CT) from POM-cluster to terpyridine ligand (D-A) along the z-axis plays the key role in the NLO response, POM-cluster (hexamolybdates) acts as a donor (D) whereas terpyridine ligand acts as an acceptor (A) in all the studied systems. The computed beta(vec) values increase by the incorporation of electron acceptors (halogen=F, Cl, Br and I) at the terminus of terpyridine ligand. Furthermore, substitution of trifluoromethoxy (-OCF(3)), trifluoromethyl (-CF(3)), and cyanide (-CN) at the end of terpyridine ligand respectively enhances the optical nonlinearity. Orbital analysis shows that the degree of CT between POM and terpyridine segment was increased in 2D and organometallic/POM hybrid systems. The present investigation provides important and thought provoking insight into the robustly large NLO properties of terpyridine-substituted hexamolybdates. |
| | |
Authors:
|
Muhammad Ramzan Saeed Ashraf Janjua; Wei Guan; Likai Yan; Zhong-Min Su; Muhammad Ali; Iftikhar Hussain Bukhari |
Related Documents
:
|
22080163 - A fishnet electrochemical hg(2+) sensing strategy based on gold nanoparticle-bioconjuga... 12870953 - Vanadium-iron-sulfur clusters containing the cubane-type [vfe3s4] core unit: synthesis ... 18197343 - Selectivity in supramolecular host-guest complexes. |
Publication Detail:
|
Type: Journal Article; Research Support, Non-U.S. Gov't Date: 2010-02-04 |
Journal Detail:
|
Title: Journal of molecular graphics & modelling Volume: 28 ISSN: 1873-4243 ISO Abbreviation: J. Mol. Graph. Model. Publication Date: 2010 Jun |
Date Detail:
|
Created Date: 2010-05-17 Completed Date: 2010-08-12 Revised Date: - |
Medline Journal Info:
|
Nlm Unique ID: 9716237 Medline TA: J Mol Graph Model Country: United States |
Other Details:
|
Languages: eng Pagination: 735-45 Citation Subset: IM |
Copyright Information:
|
Copyright (c) 2010 Elsevier Inc. All rights reserved. |
Affiliation:
|
Key Laboratory of Polyoxometalate Science of Ministry of Education, Faculty of Chemistry, Northeast Normal University, Institute of Functional Material Chemistry, Changchun 130024, Jilin, PR China. dr_janjua2010@yahoo.com |
Export Citation:
|
APA/MLA Format Download EndNote Download BibTex |
| MeSH Terms | |
Descriptor/Qualifier:
|
Computer Simulation Ligands Models, Molecular* Molecular Structure Molybdenum / chemistry* Optics and Photonics / instrumentation*, methods Pyridines / chemistry* Structure-Activity Relationship |
| Chemical | |
Reg. No./Substance:
|
0/Ligands; 0/Pyridines; 14259-85-9/molybdate; 7439-98-7/Molybdenum |
From MEDLINE®/PubMed®, a database of the U.S. National Library of Medicine
Previous Document: Off-resonance magnetisation transfer contrast (MTC) MRI using fast field-cycling (FFC).
Next Document: Genes regulated by Nkx2-3 in siRNA-mediated knockdown B cells: Implication of endothelin-1 in inflam...