Chiral crystal of a C2v-symmetric 1,3-diazaaulene derivative showing efficient optical second harmonic generation

Handle URI:
http://hdl.handle.net/10754/561728
Title:
Chiral crystal of a C2v-symmetric 1,3-diazaaulene derivative showing efficient optical second harmonic generation
Authors:
Ma, Xiaohua; Fu, Limin; Zhao, Yunfeng; Ai, Xicheng; Zhang, Jianping; Han, Yu ( 0000-0003-1462-1118 ) ; Guo, Zhixin
Abstract:
Achiral nonlinear optical (NLO) chromophores 1,3-diazaazulene derivatives, 2-(4â€-aminophenyl)-6-nitro-1,3-diazaazulene (APNA) and 2-(4â€-N,N-diphenylaminophenyl)-6-nitro-1,3-diazaazulene (DPAPNA), were synthesized with high yield. Despite the moderate static first hyperpolarizabilities (β0) for both APNA [(136 ± 5) à - 10-30 esu] and DPAPNA [(263 ± 20) à - 10-30 esu], only APNA crystal shows a powder efficiency of second harmonic generation (SHG) of 23 times that of urea. It is shown that the APNA crystallization driven cooperatively by the strong H-bonding network and the dipolar electrostatic interactions falls into the noncentrosymmetric P2 12121 space group, and that the helical supramolecular assembly is solely responsible for the efficient SHG response. To the contrary, the DPAPNA crystal with centrosymmetric P-1 space group is packed with antiparalleling dimmers, and is therefore completely SHG-inactive. 1,3-Diazaazulene derivatives are suggested to be potent building blocks for SHG-active chiral crystals, which are advantageous in high thermal stability, excellent near-infrared transparency and high degree of designing flexibility. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011 Optical crystals based on 1,3-diazaazulene derivatives are reported as the first example of organic nonlinear optical crystal whose second harmonic generation activity is found to originate solely from the chirality of their helical supramolecular orientation. The strong H-bond network forming between adjacent choromophores is found to act cooperatively with dipolar electrostatic interactions in driving the chiral crystallization of this material. Copyright © 2011 Wiley Periodicals, Inc.
KAUST Department:
Advanced Membranes and Porous Materials Research Center; Biological and Environmental Sciences and Engineering (BESE) Division; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; Nanostructured Functional Materials (NFM) laboratory
Publisher:
Wiley
Journal:
Journal of Polymer Science, Part B: Polymer Physics
Issue Date:
1-Mar-2011
DOI:
10.1002/polb.22217
Type:
Article
ISSN:
08876266
Sponsors:
Grants in aid from NSFC (Nos. 20933010 and 20911120087) and the National Basic Research Program of China (No. 2009CB220008) are acknowledged. The authors are grateful for the support from the Fundamental Research Funds for the Central Universities and the Research Funds of Renmin University of China (No. 10XNI007), and that from King Abdullah University of Science and Technology (KAUST No. 63652).
Appears in Collections:
Articles; Advanced Membranes and Porous Materials Research Center; Physical Sciences and Engineering (PSE) Division; Chemical Science Program; Biological and Environmental Sciences and Engineering (BESE) Division

Full metadata record

DC FieldValue Language
dc.contributor.authorMa, Xiaohuaen
dc.contributor.authorFu, Liminen
dc.contributor.authorZhao, Yunfengen
dc.contributor.authorAi, Xichengen
dc.contributor.authorZhang, Jianpingen
dc.contributor.authorHan, Yuen
dc.contributor.authorGuo, Zhixinen
dc.date.accessioned2015-08-03T09:03:15Zen
dc.date.available2015-08-03T09:03:15Zen
dc.date.issued2011-03-01en
dc.identifier.issn08876266en
dc.identifier.doi10.1002/polb.22217en
dc.identifier.urihttp://hdl.handle.net/10754/561728en
dc.description.abstractAchiral nonlinear optical (NLO) chromophores 1,3-diazaazulene derivatives, 2-(4â€-aminophenyl)-6-nitro-1,3-diazaazulene (APNA) and 2-(4â€-N,N-diphenylaminophenyl)-6-nitro-1,3-diazaazulene (DPAPNA), were synthesized with high yield. Despite the moderate static first hyperpolarizabilities (β0) for both APNA [(136 ± 5) à - 10-30 esu] and DPAPNA [(263 ± 20) à - 10-30 esu], only APNA crystal shows a powder efficiency of second harmonic generation (SHG) of 23 times that of urea. It is shown that the APNA crystallization driven cooperatively by the strong H-bonding network and the dipolar electrostatic interactions falls into the noncentrosymmetric P2 12121 space group, and that the helical supramolecular assembly is solely responsible for the efficient SHG response. To the contrary, the DPAPNA crystal with centrosymmetric P-1 space group is packed with antiparalleling dimmers, and is therefore completely SHG-inactive. 1,3-Diazaazulene derivatives are suggested to be potent building blocks for SHG-active chiral crystals, which are advantageous in high thermal stability, excellent near-infrared transparency and high degree of designing flexibility. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011 Optical crystals based on 1,3-diazaazulene derivatives are reported as the first example of organic nonlinear optical crystal whose second harmonic generation activity is found to originate solely from the chirality of their helical supramolecular orientation. The strong H-bond network forming between adjacent choromophores is found to act cooperatively with dipolar electrostatic interactions in driving the chiral crystallization of this material. Copyright © 2011 Wiley Periodicals, Inc.en
dc.description.sponsorshipGrants in aid from NSFC (Nos. 20933010 and 20911120087) and the National Basic Research Program of China (No. 2009CB220008) are acknowledged. The authors are grateful for the support from the Fundamental Research Funds for the Central Universities and the Research Funds of Renmin University of China (No. 10XNI007), and that from King Abdullah University of Science and Technology (KAUST No. 63652).en
dc.publisherWileyen
dc.subjectcharge transferen
dc.subjectchiralen
dc.subjectchiral organic crystalen
dc.subjectcrystal structuresen
dc.subjectdiazaazulene derivativeen
dc.subjecthyperpolarizabilityen
dc.subjectNLOen
dc.subjectnonlinear opticsen
dc.subjectnonlinear polymersen
dc.subjectsecond harmonic generationen
dc.titleChiral crystal of a C2v-symmetric 1,3-diazaaulene derivative showing efficient optical second harmonic generationen
dc.typeArticleen
dc.contributor.departmentAdvanced Membranes and Porous Materials Research Centeren
dc.contributor.departmentBiological and Environmental Sciences and Engineering (BESE) Divisionen
dc.contributor.departmentPhysical Sciences and Engineering (PSE) Divisionen
dc.contributor.departmentChemical Science Programen
dc.contributor.departmentNanostructured Functional Materials (NFM) laboratoryen
dc.identifier.journalJournal of Polymer Science, Part B: Polymer Physicsen
dc.contributor.institutionDepartment of Chemistry, Renmin University of China, Beijing 100872, Chinaen
kaust.authorZhao, Yunfengen
kaust.authorHan, Yuen
All Items in KAUST are protected by copyright, with all rights reserved, unless otherwise indicated.