Chiral crystal of a C2v-symmetric 1,3-diazaaulene derivative showing efficient optical second harmonic generation
Type
ArticleKAUST Department
Advanced Membranes and Porous Materials Research CenterBiological and Environmental Sciences and Engineering (BESE) Division
Chemical Science Program
Nanostructured Functional Materials (NFM) laboratory
Physical Science and Engineering (PSE) Division
Date
2011-03-01Online Publication Date
2011-03-01Print Publication Date
2011-05-01Permanent link to this record
http://hdl.handle.net/10754/561728
Metadata
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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.Citation
Ma, X.-H., Fu, L.-M., Zhao, Y., Ai, X.-C., Zhang, J.-P., Han, Y., & Guo, Z.-X. (2011). Chiral crystal of a C2v -symmetric 1,3-diazaaulene derivative showing efficient optical second harmonic generation. Journal of Polymer Science Part B: Polymer Physics, 49(9), 649–656. doi:10.1002/polb.22217Sponsors
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).Publisher
Wileyae974a485f413a2113503eed53cd6c53
10.1002/polb.22217