期刊
CHEMISTRY-A EUROPEAN JOURNAL
卷 14, 期 34, 页码 10628-10638出版社
WILEY-V C H VERLAG GMBH
DOI: 10.1002/chem.200801396
关键词
charge transfer; cryptands; density functional calculations; one-photon absorption; two-photon absorption
资金
- CSIR
- DRDO, New Delhi, India
- School of Chemistry, University of Birmingham
- Yonsei University [BK21]
- Ministry of Education, Science and Technology of Korea
Two-photon absorption (TPA) properties of a laterally nonsymmetric aza cryptand with attached side arms have been investigated. This series of Schiff base derivatives supports the mechanistic approach for enhancing the TPA process, which is usually dictated by molecular geometry, pi-bridging., delocalization length, and corresponding charge-transfer possibilities. The results described here suggest that on increasing the branching units, the TPA cross-section, sigma((2)), can be tuned to a larger value. The TPA activity is switched on when a metal atom enters the cavity and serves as a conduit of electronic delocalization. The sigma((2)) value increases as the donor strength increases. The maximum value is obtained on moving from the single-branched system to the nearly threefold symmetry. This serves as a useful synthetic strategy for designing, novel octupolar molecules with high sigma((2)) values. Theoretical calculations at the B3LYP functional with the 6-31G* basis Set under DFT formalism provide supporting evidence that the communication between the side arms through the metal d orbital and more ordered geometry of chromophores leads to a smaller HOMO-LUMO gap, which has a great influence upon the electronic properties of the molecules.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据